JP2001343724A - Silver halide photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photosensitive material having high sensitivity, which superior in granularity and nearly free of residual colors, after processing in rapid processing. SOLUTION: The silver halide photosensitive material contains a compound represented by formula (I) and a compound by formula (II). In the formulae, Y is, e.g. a group of atoms required for formation of heterocycle; Z1 and Z2 are each, e.g. a group of atoms required for forming an N-containing heterocycle; R, R31 and R32 are each, e.g. alkyl; D is a group required for forming a methine dye; L1, L2 and L31-L37 are each methine; p, p31 and P32 are each 0 or 1; n3 is 0, 1, 2, 3 or 4; M and M3 are each a counter ion; m and m3 are each a number 0 or larger required to neutralize electric charges in each molecule; and Z31 and Z32 are each a group of atoms required for forming an N-containing heterocycle.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic emulsion and a silver halide photographic light-sensitive material containing the emulsion. More specifically, silver halide photographic emulsions with high dissolution stability over time, and high sensitivity and excellent graininess,
It is an object of the present invention to provide a silver halide photographic light-sensitive material having less residual color even after rapid processing.

[0002]

2. Description of the Related Art It is known that sensitizing dyes used for spectral sensitization greatly affect the performance of silver halide photographic materials. Slight differences in the structure of sensitizing dyes have a significant effect on photographic performance such as sensitivity, fogging, storage stability, residual color (residual color) after processing, and granularity. The combined use of more than one species greatly affects photographic performance, but it is difficult to predict the effect in advance, and many researchers have synthesized many sensitizing dyes and Efforts have been made to examine the photographic performance of dyes in combination. However, it is still impossible to predict photographic performance. While high sensitivity and high image quality are required for photographs, demands for rapid photographic processing and reduction of waste liquid amount for environmental issues have been particularly strong in recent years, without causing adverse effects such as fogging and residual color. The importance of a technique for spectrally sensitizing silver halide grains with high sensitivity is increasing. Tabular grains have a large surface area to volume (specific surface area) and are preferred for spectral sensitization in that they can adsorb a large amount of sensitizing dyes, and are also effective in improving the sensitivity / granularity ratio. The residual (residual color) increases, and the problem of the residual color becomes more serious than the regular particles. On the other hand, in photographic processing, it is desired to reduce the processing time. However, if the processing time is reduced, the residual amount of the sensitizing dye used in the emulsion increases, and the problem of residual color becomes more serious. . Therefore,
A technique for reducing the residual color has been strongly desired. It is known that increasing the hydrophilicity of the sensitizing dye is effective as a means for improving the residual color.However, in general, the higher the hydrophilicity, the weaker the adsorption of the sensitizing dye to silver halide grains is. An adverse effect on photographic properties, such as a decrease in sensitivity, is unavoidable, and the effect of improving residual color is limited. In particular, when a large amount of sensitizing dye is added to the tabular grains, the protective colloid of gelatin is impaired by the sensitizing dye adsorbed at a high coverage. It has been clarified that the contact and coalescence of particles make aggregation more likely to occur, and that side effects such as increased fog, reduced sensitivity, and deteriorated graininess over time of the dissolution of the emulsion occur. As a solution to these problems, a substantially insoluble silver iodobromide fine grain emulsion as described in JP-A-6-332091 is used at the time of chemical sensitization of the silver halide emulsion or thereafter. Is known, but this method is not applicable to any emulsion, especially in high silver chloride emulsions, it is not applicable,
There was a need for an alternative.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide photographic emulsion having high stability over time in dissolution, and a silver halide emulsion having high sensitivity, excellent graininess, and having little residual color after processing even in rapid processing. A photographic light-sensitive material is provided.

[0004]

Means for Solving the Problems As a result of intensive studies, the object of the present invention has been achieved by the following (1) to (9). That is,

(1) In a silver halide photographic light-sensitive material containing at least one silver halide photographic emulsion layer on a support, the emulsion layer contains at least one compound represented by the following general formula (I). And at least one compound represented by the following general formula (II): General formula (I)

[0006]

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In the formula (I), Y represents a group of atoms necessary to form a heterocyclic ring or a group of atoms necessary to form a benzene ring to which a heterocyclic ring is fused; It may be condensed with a ring or may have a substituent. Z
¹ and Z ² represent an atomic group or a single bond necessary for forming a nitrogen-containing heterocyclic ring, and the nitrogen-containing heterocyclic ring has a substituent even if fused with another carbon ring or a heterocyclic ring. You may. R represents an alkyl group, an aryl group or a heterocyclic group. D represents a group necessary for forming a methine dye.
L ¹ and L ² each represent a methine group. p represents 0 or 1. M represents a counter ion, and m represents a number of 0 or more necessary to neutralize the charge in the molecule. General formula (II)

[0008]

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In the formula (II), Z³¹And Z³²Is the nitrogen-containing complex
Represents the group of atoms required to form a ring,
Even if the aromatic or non-aromatic carbon ring is fused,
But the aromatic or non-aromatic heterocyclic ring is condensed.
It does not ring. R³¹And R³²Is an alkyl group, ant
Represents a hydroxyl group or a heterocyclic group. L³¹, L³², L³³,
L ³⁴, L³⁵, L³⁶And L³⁷Represents a methine group. p³¹You
And p³²Represents 0 or 1. n^ThreeIs 0,1,2,3
Or 4 M^ThreeRepresents a counter ion and m^ThreeIs the charge in the molecule
Represents the number of zero or more necessary to neutralize the load.

(2) In the general formula (I) according to the above (1), a pyrrole ring, a furan ring, The silver halide photographic light-sensitive material according to the above (1), which represents an atom group necessary for forming a benzene ring in which a thiophene ring, a pyrrole ring, a furan ring, and a thiophene ring are fused.

(3) In the general formula (I) described in the above (1), a pyrrole ring, a furan ring, a pyrrole ring or a furan ring, wherein Y may be condensed with another carbocyclic or heterocyclic ring or may have a substituent. The silver halide photographic material as described in the above item (1), which represents an atom group necessary for forming a thiophene ring.

(4) The silver halide photographic material as described in the above item (1), wherein the general formula (I) described in the above item (1) is selected from the following general formula (Ia). General formula (Ia)

[0013]

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In the formula (Ia), Y¹¹Is a pyrrole ring, furan
Atoms necessary to form a ring, a thiophene ring, or
Indole ring, benzofuran ring, benzothiophene ring
Represents the group of atoms required to form, as well as other carbon rings
Or condensed with a heterocyclic ring or may have a substituent.
No. X¹¹Is an oxygen atom, a sulfur atom, a selenium atom or NR
¹³Represents R¹¹, R¹²And R¹³Is an alkyl group, aryl
Or a heterocyclic group. Z¹¹Forms a nitrogen-containing heterocycle
Represents a group of atoms necessary for
May be condensed with a heterocyclic ring or may have a substituent.
L¹¹, L¹², L¹³, L¹⁴And L^FifteenIs a methine group
Represents p¹Represents 0 or 1. n¹Is 0, 1, 2, 3
Or represents 4. M¹Represents a counter ion and m¹Is in the molecule
It represents a number of 0 or more necessary to neutralize the charge.
(5) The general formula (I) according to the above (1) is represented by the following general formula
The above (1), which is selected from (Ib)
Silver halide photographic material. General formula (Ib)

[0015]

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In the formula (Ib), Y ²¹ represents an atom group necessary for forming a pyrrole ring, a furan ring and a thiophene ring;
Further, it may be condensed with another carbon ring or a heterocyclic ring or may have a substituent. X ²¹ and X ²² represent an oxygen atom, a sulfur atom, a selenium atom or NR ²³ . R ²¹ , R ²² and R ²³ represent an alkyl group, an aryl group or a heterocyclic group.
V ²¹ , V ²² , V ²³ and V ²⁴ represent a hydrogen atom or a substituent, and two adjacent substituents do not combine with each other to form a saturated or unsaturated condensed ring. L ²¹ , L ²² and L ²³ each represent a methine group. n ² is 0, 1,
Represents 2, 3 or 4. M ² represents a counter ion, and m ² represents a number of 0 or more necessary to neutralize the charge in the molecule.

(6) The silver halide photograph as described in the above (1) to (5), wherein the general formula (II) as described in the above (1) to (5) is selected from the following general formula (IIa): Photosensitive material. General formula (IIa)

[0018]

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In the formula (IIa), X⁴¹And X⁴²Is oxygen source
Atom, sulfur atom, selenium atom or NR ⁴³Represents V⁴¹,
V⁴², V⁴³, V⁴⁴, V⁴⁵, V⁴⁶, V⁴⁷And V⁴⁸Is hydrogen
Represents an atom or a substituent, and two adjacent substituents are
To form a saturated or unsaturated condensed ring.
No. R⁴¹, R⁴²And R⁴³Represents an alkyl group or an aryl group.
Or a heterocyclic group. L⁴¹, L⁴²And L⁴³Is a methine group
Represents n^FourRepresents 0, 1, 2, 3, or 4. M^FourIs pair
Represents an ion, m^FourIs to neutralize the charge in the molecule
Represents the required number of 0 or more.

(7) The general formula (II) described in the above (1) to (5) is selected from the following general formula (III) or the following general formula (IV): ). General formula (III)

[0021]

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In the formula (III), X ⁵¹ and X ⁵² represent an oxygen atom or a sulfur atom. ^V51 , ^V52 , ^V53 , ^V54 , ^V55
And V ⁵⁶ represent a hydrogen atom or a substituent;
The two substituents do not combine with each other to form a saturated or unsaturated fused ring. R ⁵¹ , R ⁵² and R ⁵³ represent an alkyl group, an aryl group or a heterocyclic group. M ⁵ represents a counter ion, and m ⁵ represents a number of 0 or more necessary to neutralize the charge in the molecule. General formula (IV)

[0023]

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In the formula (IV), X ⁶¹ represents an oxygen atom or a sulfur atom. V ⁶¹ , V ⁶² , V ⁶³ , V ⁶⁴ , V ⁶⁵ and V ⁶⁶ represent a hydrogen atom or a substituent, and two adjacent substituents do not combine with each other to form a saturated or unsaturated condensed ring. . R ⁶¹ and R ⁶² represent an alkyl group, an aryl group or a heterocyclic group. M ⁶ represents a counter ion, and m ⁶ represents a number of 0 or more necessary to neutralize the charge in the molecule.

(8) In the emulsion layer as described in (1) to (7) above, 50% or more of the total projected area of the silver halide grains in the emulsion is tabular grains having an aspect ratio of 2 or more. The silver halide photographic light-sensitive material according to any one of the above (1) to (7).

(9) The silver halide photographic material as described in any of (1) to (8) above, wherein the emulsion layer in the above-mentioned (1) to (8) is selenium-sensitized. .

[0027]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below.
In the present invention, when a specific moiety is referred to as a "group", the moiety may be unsubstituted or substituted with one or more (up to the largest possible number of) substituents. Means good. For example, “alkyl group” means a substituted or unsubstituted alkyl group. The substituents that can be used in the compounds of the present invention include any substituents, regardless of whether they are substituted.

Assuming that the substituent is V, the substituent represented by V is not particularly limited. Examples thereof include a halogen atom, an alkyl group (including a cycloalkyl group and a bicycloalkyl group), and an alkenyl group (a cycloalkenyl group). , An alkynyl group), an aryl group, a heterocyclic group (also referred to as a heterocyclic group),
Cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (anilino group ), An ammonium group, an acylamino group, an aminocarbonylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfamoylamino group,
Alkyl and arylsulfonylamino groups, mercapto groups, alkylthio groups, arylthio groups, heterocyclic thio groups, sulfamoyl groups, sulfo groups, alkyl and arylsulfinyl groups, alkyl and arylsulfonyl groups, acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups , Carbamoyl group, aryl and heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, phospho group, silyl group, hydrazino group, ureido group, other known substituents As an example.

More specifically, V is a halogen atom (eg, fluorine, chlorine, bromine, iodine), an alkyl group [linear,
Represents a branched or cyclic substituted or unsubstituted alkyl group.
They include an alkyl group (preferably an alkyl group having 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl,
-Chloroethyl, 2-cyanoethyl, 2-ethylhexyl), a cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, for example, cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl), a bicycloalkyl group ( Preferably 5 to 3 carbon atoms
0 substituted or unsubstituted bicycloalkyl groups, for example, bicyclo [1.2.2] heptane-2-yl, bicyclo [2.2.2] octan-3-yl), and also a tricyclo structure having many ring structures. Includes An alkyl group (for example, an alkyl group of an alkylthio group) in the substituents described below includes the following alkenyl group, cycloalkenyl group, bicycloalkenyl group, alkynyl group, and the like in addition to the alkyl group having such a concept. ], An alkenyl group [which represents a linear, branched, or cyclic substituted or unsubstituted alkenyl group. They are alkenyl groups (preferably substituted or unsubstituted alkenyl groups having 2 to 30 carbon atoms, for example, vinyl, allyl, prenyl, geranyl, oleyl), cycloalkenyl groups (preferably substituted or unsubstituted 3 to 30 carbon atoms). Cycloalkenyl groups such as 2-cyclopenten-1-yl, 2-cyclohexen-1-yl), bicycloalkenyl groups (substituted or unsubstituted bicycloalkenyl groups, preferably substituted or unsubstituted bicycloalkenyl having 5 to 30 carbon atoms) Groups such as bicyclo [2.2.1] hept-2-ene-
1-yl, bicyclo [2.2.2] oct-2-ene-
4-yl). An alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms such as ethynyl, propargyl, trimethylsilylethynyl group), an aryl group (preferably having 6 carbon atoms)
~ 30 substituted or unsubstituted aryl groups such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, o
-Hexadecanoylaminophenyl), a heterocyclic group (preferably a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound obtained by removing one hydrogen atom from a monovalent group, More preferably, it has 3 to 30 carbon atoms.
A 5- or 6-membered aromatic heterocyclic group such as 2-furyl, 2
-Thienyl, 2-pyrimidinyl, 2-benzothiazolyl, still 1-methyl-2-pyridinio, 1-methyl-2
A cationic heterocyclic group such as quinolinio),

A cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group (preferably having 1 to 3 carbon atoms)
0 substituted or unsubstituted alkoxy group such as methoxy, ethoxy, isopropoxy, t-butoxy, n-octyloxy, 2-methoxyethoxy), aryloxy group (preferably substituted or unsubstituted having 6 to 30 carbon atoms) Aryloxy group such as phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy), silyloxy group (preferably silyloxy group having 3 to 20 carbon atoms, such as trimethylsilyloxy , T-butyldimethylsilyloxy), a heterocyclic oxy group (preferably a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms, such as 1-phenyltetrazole-5-oxy,
-Tetrahydropyranyloxy), an acyloxy group (preferably a formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, and a carbon number of 6 to 6)
30 substituted or unsubstituted arylcarbonyloxy groups such as formyloxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy, p
-Methoxyphenylcarbonyloxy), a carbamoyloxy group (preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, such as N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, , N-di-n-
Octylaminocarbonyloxy, Nn-octylcarbamoyloxy), alkoxycarbonyloxy group (preferably substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, for example, methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy , N-octylcarbonyloxy), an aryloxycarbonyloxy group (preferably having 7 to 7 carbon atoms)
30 substituted or unsubstituted aryloxycarbonyloxy groups such as phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy),

An amino group (preferably an amino group having 1 carbon atom)
A substituted or unsubstituted alkylamino group having from 30 to 30 carbon atoms, a substituted or unsubstituted anilino group having 6 to 30 carbon atoms, such as amino, methylamino, dimethylamino, anilino, N
-Methylanilino, diphenylamino), an ammonio group (preferably an ammonio group, a substituted or unsubstituted alkyl or aryl having 1 to 30 carbon atoms, an ammonio group substituted with a heterocycle, for example, trimethylammonio, triethylammonio, diphenylmethylammonium E), an acylamino group (preferably a formylamino group, having 1 to 3 carbon atoms)
0 substituted or unsubstituted alkylcarbonylamino group, 6 to 30 carbon atoms of substituted or unsubstituted arylcarbonylamino group, for example, formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, 3,4,5-tri -N-octyloxyphenylcarbonylamino), an aminocarbonylamino group (preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms, for example, carbamoylamino,
N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino), alkoxycarbonylamino group (preferably substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, such as methoxycarbonylamino, ethoxy Carbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methylmethoxycarbonylamino), an aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, for example, Phenoxycarbonylamino, p-chlorophenoxycarbonylamino, m- (n-octyloxyphenoxycarbonylamino), sulfamoylamino group (preferably having 0 to 3 carbon atoms) A substituted or unsubstituted sulfamoylamino group, such as sulfamoylamino, N, N
-Dimethylaminosulfonylamino, Nn-octylaminosulfonylamino), alkyl and arylsulfonylamino groups (preferably substituted or unsubstituted alkylsulfonylamino groups having 1 to 30 carbon atoms, 6 carbon atoms)
~ 30 substituted or unsubstituted arylsulfonylamino groups such as methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamino),

A mercapto group, an alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, for example, methylthio, ethylthio, n-hexadecylthio), an arylthio group (preferably substituted or unsubstituted having 6 to 30 carbon atoms) Arylthio group, for example, phenylthio, p-chlorophenylthio, m-methoxyphenylthio), a heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, for example, 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio), a sulfamoyl group (preferably having 0 to 30 carbon atoms)
A substituted or unsubstituted sulfamoyl group such as N-
Ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N, N-dimethylsulfamoyl, N-acetylsulfamoyl, N-benzoylsulfamoyl, N- (N'-phenylcarbamoyl) sulfamoyl) , A sulfo group, an alkyl and arylsulfinyl group (preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms such as methylsulfinyl, ethylsulfinyl, phenylsulfinyl,
p-methylphenylsulfinyl), alkyl and arylsulfonyl groups (preferably substituted or unsubstituted alkylsulfonyl groups having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonyl groups having 6 to 30 carbon atoms, such as methylsulfonyl, ethylsulfonyl, Phenylsulfonyl, p
-Methylphenylsulfonyl), an acyl group (preferably a formyl group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, and 4 to 30 carbon atoms. A heterocyclic carbonyl group bonded to a carbonyl group by a substituted or unsubstituted carbon atom such as acetyl, pivaloyl,
2-chloroacetyl, stearoyl, benzoyl, p-
n-octyloxyphenylcarbonyl, 2-pyridylcarbonyl, 2-furylcarbonyl), an aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, for example, phenoxycarbonyl, o-chlorophenoxycarbonyl) , M
-Nitrophenoxycarbonyl, pt-butylphenoxycarbonyl), an alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxy Carbonyl), carbamoyl group (preferably having 1 carbon atom)
Up to 30 substituted or unsubstituted carbamoyl groups such as carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl),

Aryl and heterocyclic azo groups (preferably substituted or unsubstituted arylazo groups having 6 to 30 carbon atoms, substituted or unsubstituted heterocyclic azo groups having 3 to 30 carbon atoms, for example, phenylazo, p-chlorophenylazo,
5-ethylthio-1,3,4-thiadiazol-2-ylazo), an imide group (preferably N-succinimide,
N-phthalimido), a phosphino group (preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, for example, dimethylphosphino, diphenylphosphino, methylphenoxyphosphino), a phosphinyl group (preferably having 2 to 30 carbon atoms) A substituted or unsubstituted phosphinyl group,
For example, phosphinyl, dioctyloxyphosphinyl,
Diethoxyphosphinyl), a phosphinyloxy group (preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, such as diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy), phosphinyl Amino group (preferably a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, for example, dimethoxyphosphinylamino, dimethylaminophosphinylamino), a phospho group, a silyl group (preferably having 3 to 30 carbon atoms). 30
A substituted or unsubstituted silyl group such as trimethylsilyl, t-butyldimethylsilyl and phenyldimethylsilyl), a hydrazino group (preferably a substituted or unsubstituted hydrazino group having 0 to 30 carbon atoms such as trimethylhydrazino), a ureido group (Preferably a substituted or unsubstituted ureido group having 0 to 30 carbon atoms, for example, N, N-dimethylureido).

Further, two Vs are connected to each other to form a ring (aromatic or non-aromatic hydrocarbon ring or heterocyclic ring. These can be further combined to form a polycyclic fused ring, for example, a benzene ring. , Naphthalene ring, anthracene ring, quinoline ring, phenanthrene ring, fluorene ring, triphenylene ring, naphthacene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring,
Pyrimidine ring, pyridazine ring, indolizine ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, quinoline ring, carbazole ring, phenanthate Lysine ring, acridine ring, phenanthroline ring, thianthrene ring, chromene ring, xanthene ring, phenoxathiin ring,
And a phenothiazine ring and a phenazine ring. ) May have a condensed structure.

Among the above substituents V, those having a hydrogen atom may be removed therefrom and further substituted with the above substituents. Examples of such complex substituents include acylsulfamoyl groups, alkyl and arylsulfonylcarbamoyl groups. Examples include methylsulfonylcarbamoyl, p-methylphenylsulfonylcarbamoyl, acetylsulfamoyl, benzoylsulfamoyl groups.

Hereinafter, the methine dye represented by formula (I) of the present invention will be described in detail. When Y is a group of atoms necessary for forming a heterocyclic ring, the 5-membered unsaturated heterocyclic ring formed by Y is a pyrrole ring, a pyrazole ring, an imidazole ring, a triazole ring, a furan ring, an oxazole ring, an isoxazole ring. Ring, thiophene ring, thiazole ring, isothiazole ring, thiadiazole ring, selenophene ring, selenazole ring, isoselenazole ring, tellurophen ring, tellurazole ring, isotellurazole ring, etc.
Examples of the membered unsaturated heterocyclic ring include a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a pyran ring, a thiopyran ring and the like, and further condensed with another 5- to 6-membered carbon ring or heterocyclic ring, for example, An indole ring, a benzofuran ring, a benzothiophene ring, and a thienothiophene ring can also be formed. Further, unsaturated heterocycles in which part of the double bond in these heterocycles is hydrogenated (for example, a pyrroline ring, a pyrazoline ring, an imidazoline ring, a dihydrofuran ring, an oxazoline ring, a dihydrothiophene ring, a thiazoline ring),
Alternatively, it may be a hydrogenated saturated heterocycle (for example, pyrrolidine ring, pyrazolidine ring, imidazolidine ring, tetrahydrofuran ring, oxazolidine ring, tetrahydrothiophene ring, thiazolidine ring). When Y is an atomic group necessary to form a benzene ring to which a heterocyclic ring is fused, examples of the ring formed by Y include an indole ring, a benzofuran ring, and a benzothiophene ring.

The ring formed by Y is preferably a pyrrole ring, a furan ring, a thiophene ring, an indole ring, a benzofuran ring or a benzothiophene ring, more preferably a pyrrole ring, a thiophene ring or a furan ring.

The nitrogen-containing heterocyclic ring formed by Z ¹ and Z ² is preferably a 5- or 6-membered nitrogen-containing heterocyclic ring, and may be an oxazole ring, a thiazole ring, a selenazole ring, an imidazole ring, a 2-pyridine ring, -Pyridine ring and 3,3-dimethyl-3H-pyrrole ring. In addition to the ring represented by Y, a benzene ring, a cyclohexene ring,
A carbon ring such as a naphthalene ring or a heterocyclic ring such as a furan ring or a thiophene ring may be condensed. The nitrogen-containing heterocyclic ring formed by Z ¹ and Z ² is more preferably an oxazole ring, a thiazole ring, an imidazole ring and a 2-pyridine ring, and further preferably an oxazole ring and a thiazole ring.

The ring formed by Y and the nitrogen-containing heterocyclic ring formed by Z ¹ and Z ² may have a substituent, and the substituent represented by V is mentioned as an example. .
Preferred substituents V are the above-mentioned alkyl groups, aryl groups, aromatic heterocyclic groups, alkoxy groups, alkylthio groups, cyano groups, and halogen atoms.

The alkyl group represented by R may be unsubstituted or substituted, and has 1 to 18 carbon atoms, preferably 1 to 18 carbon atoms.
7, particularly preferably 1 to 4 unsubstituted alkyl groups (for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, dodecyl, octadecyl) or 1 to 18 carbon atoms, preferably 1 to 4
7, particularly preferably 1-4 substituted alkyl groups ｛substituents, each substituent represented by the above-mentioned V (aryl group, unsaturated hydrocarbon group, carboxy group, sulfo group, sulfato group, cyano group, halogeno Atom (for example, fluorine, chlorine, bromine, iodine), hydroxy group, mercapto group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, carbamoyl group, sulfamoyl group , A heterocyclic group, an alkylsulfonylcarbamoyl group, an acylcarbamoyl group, an acylsulfamoyl group, an alkylsulfonylsulfamoyl group, and the like, which may be further substituted).

The aryl group represented by R may be unsubstituted or substituted, and has 6 to 20 carbon atoms, preferably 6 to 15 carbon atoms, and more preferably 6 to 10 carbon atoms. Phenyl, 1-naphthyl) or a substituted aryl group having 6 to 26 carbon atoms, preferably 6 to 21 carbon atoms, and more preferably 6 to 16 carbon atoms. Alkyl and aryl groups, unsaturated hydrocarbon groups, carboxy groups, sulfo groups,
A sulfato group, a cyano group, a halogen atom (eg, fluorine, chlorine, bromine, iodine), a hydroxy group, a mercapto group, an alkoxy group, an aryloxy group, an alkylthio group,
Arylthio group, acyl group, alkoxycarbonyl group,
An aryloxycarbonyl group, an acyloxy group, a carbamoyl group, a sulfamoyl group, a heterocyclic group, an alkylsulfonylcarbamoyl group, an acylcarbamoyl group, an acylsulfamoyl group, an alkylsulfonylsulfamoyl group, which may be further substituted). ｝
Preferably it is a phenyl group.

The heterocyclic group represented by R may be unsubstituted or substituted and has 1 to 20 carbon atoms, preferably 1 carbon atom.
To 15, more preferably an unsubstituted heterocyclic group having 1 to 10 carbon atoms (e.g., pyrrole, furan, thiophene), or 1 to 26 carbon atoms, preferably 1 to 21 carbon atoms, and more preferably 1 to 16 carbon atoms. Substituted heterocyclic groups {Examples of the substituent include the respective substituents represented by V above}.

R is preferably an acid group or a group having a dissociable proton, such as a carboxyl group, a sulfo group,
A phosphonic acid group, a boronic acid group, or -CONHSO _{2
-, - SO 2 NHSO 2 -} , - CONHCO -, - SO 2
NHCO- or the like, is more preferably a carboxyl group, a sulfo group, an alkylsulfonylcarbamoyl group (eg, methanesulfonylcarbonyl), an acylcarbamoyl group (eg, acetylcarbamoyl), an acylsulfamoyl group (eg, acetylsulfa Moyl) or an alkylsulfonylsulfamoyl group (eg, methanesulfonylsulfamoyl). More preferably, they are a carboxymethyl group, a 2-sulfoethyl group, a 3-sulfopropyl group, a 3-sulfobutyl group, a 4-sulfobutyl group, or a methanesulfonylcarbamoylmethyl group.

The methine groups represented by L ¹ and L ² may have a substituent. Examples of the substituent include the substituents represented by V. p is preferably 0.

M in the general formula (I) is included in the formula to indicate the presence of a cation or an anion when necessary to neutralize the ionic charge of the dye. Whether a dye is a cation, an anion, or has a net ionic charge depends on its substituents and the environment (such as pH) in the solution. Typical cations include inorganic cations such as hydrogen ion (H ⁺ ), alkali metal ions (eg, sodium ion, potassium ion, lithium ion), alkaline earth metal ions (eg, calcium ion), and ammonium ions (eg, Organic ions such as ammonium ion, tetraalkylammonium ion, triethylammonium ion, pyridinium ion, ethylpyridinium ion, 1,8-diazabicyclo [5.4.0] -7-undecenium ion). The anion may be either an inorganic anion or an organic anion, such as a halide anion (eg, fluoride ion, chloride ion, bromide ion, iodide ion), or a substituted aryl sulfonate ion (eg, p-ion). Toluenesulfonic acid ion, p-chlorobenzenesulfonic acid ion, aryldisulfonic acid ion (for example, 1,3-benzenesulfonic acid ion,
1,5-naphthalenedisulfonic acid ion, 2,6-naphthalenedisulfonic acid ion), alkyl sulfate ion (for example, methyl sulfate ion), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion,
Examples include picrate ion, acetate ion, and trifluoromethanesulfonic acid ion. In addition, other dyes having an opposite charge to the ionic polymer or dye may be used. Preferred cations are sodium ion, potassium ion, triethylammonium ion, tetraethylammonium ion, pyridinium ion, ethylpyridinium ion, methylpyridinium ion. Preferred anions are perchlorate, iodide, bromide, substituted arylsulfonate (eg p.
-Toluenesulfonate ion). m represents a number of 0 or more necessary to balance the charges, and is 0 when an internal salt is formed. It is preferably a number from 0 to 4.

D is a group necessary for forming a methine dye, and any methine dye can be formed by D. Preferably, cyanine dye, merocyanine dye, rhodacyanine dye, trinuclear merocyanine dye, Examples include a nuclear merocyanine dye, an allopolar dye, a hemicyanine dye, and a styryl dye. For more information on these dyes, see FM Hemer's Heterocyclic Compounds-
Cyanine Dyes and Related Compounds, '' John Wiley &
Sons-New York, London, 1964, D.
M. Sturmer, Heterocyclic Compounds-Special topics
in heterocyclicchemistry ", Chapter 18, Section 14,
482-515 and the like. Preferred general formulas of the dyes include the general formulas described in U.S. Pat. No. 5,994,051, columns 32-36, and US Pat.
No. 236, columns 30 to 34. The general formulas of cyanine dyes, merocyanine dyes and rhodacyanine dyes are described in US Pat. No. 5,340,694 No. 21.
(XI), (XII), and (XIII) in columns 22 to 22 (however, the number of n ₁₂ , n ₁₅ , n ₁₇ , and n ₁₈ is not limited;
An integer greater than or equal to 4 (preferably 4 or less) is preferred. Preferred are cyanine, merocyanine and rhodacyanine dyes, and more preferred are cyanine dyes.

In the general formula (I), when a cyanine dye is formed by D, it can be represented by a resonance formula such as the following general formula (I '). General formula (I ')

[0048]

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Preferred examples of the compound represented by the formula (I) are more specifically exemplified. More preferably, the compound of the general formula (I) is selected from the following general formulas (a) to (l).

[0050]

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In the formula, D, R, M and m have the same meanings as those in formula (I), and X ¹ is an oxygen atom, a sulfur atom, a selenium atom or NR ¹ (R ¹ is an alkyl group, an aryl group X ² represents an oxygen atom, a sulfur atom or N 2
R ² (R ² is an alkyl group, an aryl group or a heterocyclic group). Further, the benzene ring and the heterocyclic ring in the formula may be substituted with each substituent represented by V, and may be condensed with another carbon ring or a heterocyclic ring. Among these, preferred are (a) to (i), and more preferred are (a) to (a).
(F), more preferably (a) to (c), and particularly preferably (a) or (c).

More preferably, the methine dyes represented by the general formula (I) are represented by the following general formulas (XI), (XII) and (XII)
This is the case where the methine dye is selected from I) and (XIV). General formula (XI)

[0053]

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In the formula (XI), Y, R, Z ¹ , Z ² , L ¹ ,
L ² and p have the same meanings as in formula (I), and L ⁷¹ , L ⁷² , L ⁷³ ,
L ⁷⁴ and L ⁷⁵ represent a methine group. p ⁷ represents 0 or 1. n ⁷ represents 0, 1, 2, 3, or 4. Y ⁷¹ is 5
Represents an atom group necessary for forming a 6- to 6-membered nitrogen-containing heterocyclic ring, and may further have a condensed or substituted substituent on another carbon ring or heterocyclic ring. M ⁷ represents a counter ion and m ⁷
Represents a number of 0 or more and 4 or less necessary for neutralizing the electric charge of the molecule. R ⁷¹ represents a substituted or unsubstituted alkyl group, aryl group, or heterocyclic group. General formula (XII)

[0055]

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In the formula (XII), Y, R, Z ¹ , Z ² , L ¹ , L
^2, p is as defined for formula (I), L ^{8 1} and L ⁸² each represents a methine group. n ⁸ represents 0, 1, 2, 3, or 4. Y
⁸¹ represents an atom group necessary for forming an acidic nucleus, and may be further condensed with another carbon ring or a heterocyclic ring or may have a substituent. M ⁸ represents a counter ion, and m ⁸ represents a number of 0 or more and 4 or less necessary for neutralizing the charge of the molecule. General formula (XIII)

[0057]

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In the formula (XIII), Y, R, Z¹, Z^Two, L¹,
L^Two, P has the same meaning as in formula (I), ⁹¹, L⁹², L⁹³,
L⁹⁴, L⁹⁵, L⁹⁶And L⁹⁷Represents a methine group. p⁹Is
Represents 0 or 1. n⁹¹And n⁹²Is 0,1,2,3
Or 4 Y⁹¹And Y⁹²Is a 5- to 6-membered nitrogen-containing complex
Represents an atomic group necessary to form a ring, and has a substituent
It may be. Where Y⁹²Has another carbocycle or
The heterocycle may be fused. M⁹Represents a counter ion,
m⁹Is from 0 to 4 required to neutralize the molecular charge
Represents a number. R⁹¹And R⁹²Is substituted or unsubstituted
Represents an alkyl group, an aryl group, or a heterocyclic group. General formula (XIV)

[0059]

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In the formula (XIV), Y, R, Z ¹ , Z ² , L ¹ , L
^2, p is as defined for formula ^{(I), L 1 01,} L 102, L 103,
L ¹⁰⁴ , L ¹⁰⁵ , L ¹⁰⁶ and L ¹⁰⁷ represent a methine group. p
¹⁰ represents 0 or 1. n ¹⁰¹ and n ¹⁰² are 0, 1,
Represents 2, 3 or 4. Y ¹⁰¹ and Y ¹⁰² represent an atomic group necessary for forming a 5- to 6-membered nitrogen-containing heterocyclic ring, and may have a substituent. However, Y ¹⁰² may be further fused with another carbocyclic or heterocyclic ring. M ¹⁰ represents a counter ion, and m ¹⁰ represents 0 required to neutralize the molecular charge.
Represents a number from 4 to 4. R ¹⁰¹ and R ¹⁰² represent a substituted or unsubstituted alkyl group, aryl group, or heterocyclic group.

The 5- to 6-membered nitrogen-containing heterocyclic ring represented by Y ⁷¹ , Y ⁹² and Y ¹⁰² in the general formulas (XI), (XII), (XIII) and (XIV) is It may be condensed with a 6-membered carbocyclic or heterocyclic ring. Examples of the carbocycle include a benzene ring and a naphthalene ring, and examples of the heterocycle include a furan ring and a thiophene ring. The condensed ring is preferably a carbocycle, and more preferably a benzene ring. Specifically, 5- or 6-membered nitrogen-containing heterocyclic ring (system) are preferred mentioned as examples of Z ¹¹ in formula described below (Ia), as specific examples, the U.S. Patent No. 5,340,694 23 ~ 24
The same as those mentioned as examples of Z ₁₁ , Z ₁₂ , Z ₁₃ , Z ₁₄ and Z _{16 in} the column can be mentioned.

Y ⁸¹ represents a group of atoms necessary for forming an acyclic or cyclic acidic nucleus, and can take the form of an acidic nucleus of any general merocyanine dye. Next to the methine chain linking the position of the Y ⁸¹ are a thiocarbonyl group or a carbonyl group in a preferred form. The acidic nucleus referred to here is, for example, “The Theory of the Photo” edited by TH James.
Graphic Process ", 4th edition, published by MacMillan Publishing, 1977, p. 198. Specifically, U.S. Patent Nos. 3,567,719 and 3,57
5,869, 3,804,634, 3,8
No. 37,862, No. 4,002,480, No. 4,
925,777 and JP-A-3-167546. The acidic nucleus is preferable when it forms a 5- to 6-membered nitrogen-containing heterocyclic ring composed of carbon, nitrogen and chalcogen (typically oxygen, sulfur, selenium and tellurium) atoms.

2-pyrazolin-5-one, pyrazolidin-3,5-dione, imidazolin-5-one, hydantoin, 2- or 4-thiohydantoin, 2-iminooxazolidin-4-one, 2-oxazoline-5-one ,
2-thiooxazoline-2,4-dione, isoxazolin-5-one, 2-thiazolin-4-one, thiazolidine-4-one, thiazolidine-2,4-dione, rhodanine, thiazolidine-2,4-dithione, Isorhodanine, indan-1,3-dione, thiophen-3-one, thiophen-3-one-1,1-dioxide, indoline-2-one, indoline-3-one, 2-oxoindazolinium, 3-oxo Indazolinium, 5,
7-dioxo-6,7-dihydrothiazolo [3,2-
a] pyrimidine, cyclohexane-1,3-dione,
3,4-dihydroisoquinolin-4-one, 1,3-dioxane-4,6-dione, barbituric acid, 2-thiobarbituric acid, chroman-2,4-dione, indazolin-2-one, pyrido [ 1,2-a] pyrimidine-
1,3-dione, pyrazolo [1,5-b] quinazolone,
Pyrazolo [1,5-a] benzimidazole, pyrazolopyridone, 1,2,3,4-tetrahydroquinoline-
2,4-dione, 3-oxo-2,3-dihydrobenzo [d] thiophene-1,1-dioxide, 3-dicyanomethylene-2,3-dihydrobenzo [d] thiophene-
1,1-dioxide nuclei; and nuclei having an exomethylene structure in which the carbonyl group or thiocarbonyl group forming these nuclei is substituted with an active methylene position of an active methylene compound having a structure such as ketomethylene or cyanomethylene.

[0064] Preferably hydantoin as Y ^81, 2 or 4-thiohydantoin, 2-oxazolin-5-one, 2-thio-oxazoline-2,4-dione, thiazolidine-2,4-dione, rhodanine, thiazolidine -
2,4-dithione, barbituric acid and 2-thiobarbituric acid, more preferably hydantoin, 2 or 4-thiohydantoin, 2-oxazoline-5-one, rhodanine, barbituric acid, 2-thiobarbitic acid Tool acid. Particularly preferred are 2 or 4-thiohydantoin, 2-oxazolin-5-one, rhodanine and barbituric acid.

5 formed by Y ⁹¹ and Y ¹⁰¹
The 6-membered nitrogen-containing heterocyclic ring is obtained by removing an oxo group or a thioxo group from the heterocyclic ring represented by Y ⁸¹ . Preferably, hydantoin, 2 or 4-thiohydantoin, 2-oxazolin-5-one, 2-thiooxazoline-2,4-dione, thiazolidine-2,4-dione,
Rhodanine, thiazolidine-2,4-dithione, barbituric acid, 2-thiobarbituric acid obtained by removing an oxo group or a thioxo group, more preferably,
Hydantoin, 2 or 4-thiohydantoin, 2-oxazolin-5-one, rhodanine, barbituric acid,
2-thiobarbituric acid obtained by removing an oxo group or a thioxo group, particularly preferably 2- or 4-thiohydantoin, 2-oxazoline-5-one, or rhodanine obtained by removing an oxo group or a thioxo group. It is.

R ⁷¹ , R ⁹¹ , R ⁹² , R ¹⁰¹ , R ¹⁰² and the substituent on the nitrogen atom of the acidic nucleus Y ⁸¹ (if any, R ⁸¹ ) are each a substituted or unsubstituted alkyl group. ,
The group which represents an aryl group or a heterocyclic group and which is mentioned as an example of R in the methine dye of the general formula (I) is preferable. R ⁷¹ , R
Of these, ⁸¹ , R ⁹¹ , R ⁹² , R ¹⁰¹ and R ¹⁰² are preferably a substituted or unsubstituted alkyl group, more preferably an alkyl group substituted by an acid group or a group having a dissociable proton. More preferably a carboxyl group, a sulfo group or _{-CONHSO 2, -, - SO 2} NHSO
_{2 -, - CONHCO -, -} SO 2 NHCO- substituted alkyl groups containing any one of, particularly preferably,
A carboxymethyl group, a 2-sulfoethyl group, a 3-sulfopropyl group, a 3-sulfobutyl group, a 4-sulfobutyl group, or a methanesulfonylcarbamoylmethyl group.

L ⁷¹ , L ⁷² , L ⁷³ , L ⁷⁴ , L ⁷⁵ , L ⁸¹ , L
⁸² , ^L91 , ^L92 , ^L93 , ^L94 , ^L95 , ^L96 , ^L97 , L
¹⁰¹ , ^L102 , ^L103 , ^L104 , ^L105 , ^L106 and ^L107
Each independently represents a methine group. These methine groups may have a substituent, and examples of the substituent include the substituents represented by V. It may also form a ring with another methine group, or Y ⁷¹ , Y ⁸¹ , Y ⁹¹ , Y ⁹² , Y
^101, Y ¹⁰² together may also form a ring. L ¹ ,
L ² , L ⁷⁴ , L ⁷⁵ , L ⁹⁶ , L ⁹⁷ , L ¹⁰⁶ and L ¹⁰⁷ are preferably unsubstituted methine groups.

N ⁷ , n ⁸ , n ⁹¹ , n ⁹² , n ¹⁰¹ and n ¹⁰²
Represents 0, 1, 2, 3 or 4, and when it is 2 or more, the methine group is repeated, but need not be the same. n ⁷ , n ⁸ ,
n ⁹¹ and n ¹⁰² are preferably 0, 1, 2, 3, more preferably 0, 1, 2 and particularly preferably 0 or 1. n ⁹² and n ¹⁰¹ are preferably 0 or 1, and more preferably 0.

P ⁷ , p ⁹ and p ¹⁰ each independently represent 0 or 1. Preferably it is 0.

Each of M ⁷ , M ⁸ , M ⁹ and M ¹⁰ represents a counter ion, and is preferably the same as the above-mentioned M. m ⁷ , m ⁸ ,
m ⁹ and m ¹⁰ are 0 required to neutralize the charge in the molecule.
It represents the above number, and is 0 when an internal salt is formed. It is preferably a number from 0 to 4.

The methine dye represented by the general formula (I) is particularly preferably a cyanine dye (XI) among the general formulas (XI), (XII), (XIII) and (XIV),
(XI) is more preferably represented by the general formula (Ia). Hereinafter, the dye represented by Formula (Ia) will be described in detail.

In the general formula (Ia), Y ¹¹ represents an atom group necessary for forming a pyrrole ring, a furan ring or a thiophene ring, or an atom group necessary for forming an indole ring, a benzofuran ring or a benzothiophene ring. Which may be condensed with another carbon ring or a heterocyclic ring or may have a substituent, but it is preferable that no other condensed ring is present. The ring formed by Y ¹¹ is particularly preferably a pyrrole ring, a furan ring or a thiophene ring.

[0073] X ¹¹ is an oxygen atom, a sulfur atom, represents a selenium atom or NR ^13, oxygen atom, sulfur atom or NR ¹³
And particularly preferably an oxygen atom or a sulfur atom.

The nitrogen-containing heterocyclic ring formed by Z ¹¹ may be condensed with a carbon ring such as a benzene ring, a cyclohexene ring or a naphthalene ring or a heterocyclic ring such as a furan ring or a thiophene ring. Is preferably a carbocyclic ring, more preferably a benzene ring. Nitrogen-containing heterocyclic ring is preferably formed by Z ^11, thiazoline ring, thiazole ring, benzothiazole ring, an oxazoline ring, an oxazole ring, benzoxazole ring, selenazoline ring, selenazole ring, benzoselenazole ring, Terurazorin ring, tellurazole ring Benzotellurazole ring, 3,3-dialkylindolenine ring (eg, 3,3-dimethylindolenine), imidazoline ring, imidazole ring, benzimidazole ring, isoxazole ring, isothiazole ring, pyrazole ring, 2-pyridine ring , 4-pyridine ring, 2-quinoline ring, 4-quinoline ring, 1-isoquinoline ring, 3-
Examples include an isoquinoline ring, an imidazo [4,5-b] quinoxalin ring, an oxadiazole ring, a thiadiazole ring, a tetrazole ring, a pyrimidine ring, and a ring obtained by condensing a benzene ring with the above ring. More preferred are a benzoxazole ring, a benzothiazole ring, a benzimidazole ring and a quinoline ring, and still more preferred are a benzoxazole ring and a benzothiazole ring. These may be substituted by the respective substituents represented by V described above. Specific examples include those similar to the examples of Z ₁₁ , Z ₁₂ , Z ₁₃ , Z ₁₄ and Z ₁₆ in U.S. Pat. No. 5,340,694, columns 23 to 24.

R¹¹, R¹², R¹³An alkyl group represented by
Examples of the aryl group and the heterocyclic group include the methyl group represented by the general formula (I).
Examples of the groups described for R in the dye include:
R¹¹, R¹²Preferably has an acid group or a dissociable proton.
Is a substituted alkyl group, more preferably
Carboxyl group, sulfo group, or -CONHSO _Two
-, -SO_TwoNHSO_Two-, -CONHCO-, -SO_Two
NHCO- is a substituted alkyl group containing any of
And particularly preferably a 2-sulfoethyl group, a 3-sulfoethyl group.
Propyl group, 3-sulfobutyl group, 4-sulfobutyl
Group, carboxymethyl group or methanesulfonylcarba
Moylmethyl group. R¹³Is preferably unsubstituted alkyl
Especially a methyl group or an ethyl group.
preferable.

The methine groups represented by L ¹¹ , L ¹² , L ¹³ , L ¹⁴ and L ¹⁵ may be unsubstituted or substituted, and examples of the substituent include the substituents represented by V. L ¹⁴ , L
¹⁵ is preferably both unsubstituted methine groups.

N ¹ represents 0, ¹ , 2, 3 or 4;
In the above case, the methine group is repeated, but need not be the same. It is preferably 0, 1, 2, 3, more preferably 0, 1, 2, and even more preferably 0 or 1. p ¹ represents 0 or 1, and is preferably 0.

Examples of M ¹ include the respective ions described for M in the methine dye of formula (I).
Particularly, it is preferably a cation. Preferred cations are sodium, potassium, triethylammonium, pyridinium, N-ethylpyridinium. m ¹ represents a number of 0 or more necessary for neutralizing an intramolecular charge, and is 0 when an intramolecular salt is formed. Preferably it is 0, 1, 2, or 3.

The methine dye represented by the general formula (Ia) is more preferably represented by the general formula (Ib). Hereinafter, the dye represented by formula (Ib) will be described in detail.

In the general formula (Ib), Y^{twenty one}Formed by
Ring is selected from a pyrrole ring, a furan ring, and a thiophene ring.
You. Y^{twenty one}The direction of condensation of the ring formed by is arbitrary,
Taking the case of the thiophene ring as an example, the sulfur of the thiophene ring
The atom is X to the fused carbon-carbon bond^{twenty one}On the same side as
Thieno [3,2-d] azole type (of the above general formula (c)
Type) or X ^{twenty one}Thieno [2,3-
d] azole type (type of the above general formula (a)), thiol
Thieno [3,4-d] azo fused at the 3- and 4-positions of the benzene ring
Of the general formula (type of the general formula (b))
Is preferred. Long wavelength spectral absorption is required as a sensitizing dye
In particular, the type of the general formula (a) is preferable.
Further Y^{twenty one}May have a substituent on the ring formed by
Preferably, each substituent represented by V is a substituent.
No. The substituent may be an alkyl group (eg, methyl),
Reel groups (eg, phenyl), aromatic heterocyclic groups (eg,
1-pyrrolyl), an alkoxy group (for example, methoxy),
Alkylthio group (eg methylthio), cyano group, halogen
Atom (for example, fluorine, chlorine, bromine, iodine)
And more preferably a halogen atom.
Is preferably a chlorine atom or a bromine atom.

X ²¹ and X ²² represent an oxygen atom, a sulfur atom, a selenium atom or NR ²³ , preferably an oxygen atom, a sulfur atom or NR ²³ , more preferably an oxygen atom or a sulfur atom, It is preferably a sulfur atom.

R^{twenty one}, R^{twenty two}, R^{twenty three}An alkyl group represented by
Examples of the aryl group and the heterocyclic group include the methyl group represented by the general formula (I).
Examples of the groups described for R in the dye include:
R^{twenty one}, R^{twenty two}Preferably has an acid group or a dissociable proton.
Is a substituted alkyl group, more preferably
Carboxyl group, sulfo group, or -CONHSO _Two
-, -SO_TwoNHSO_Two-, -CONHCO-, -SO_Two
NHCO- is a substituted alkyl group containing any of
And particularly preferably a 2-sulfoethyl group, a 3-sulfoethyl group.
Propyl group, 3-sulfobutyl group, 4-sulfobutyl
Group, carboxymethyl group or methanesulfonylcarba
Moylmethyl group. More preferably, R^{twenty one}, R^{twenty two}
Is a 2-sulfoethyl group, 3-sulfopro
Pill group, 3-sulfobutyl group or 4-sulfobutyl group
And the other is a carboxymethyl group or a methanes group.
It is a rufonylcarbamoylmethyl group. R^{twenty three}Is preferably
Is an unsubstituted alkyl group, and is a methyl group or an ethyl group.
It is particularly preferred that there is.

The substituents represented by V ²¹ , V ²² , V ²³ , and V ²⁴ include the substituents represented by V, and two adjacent substituents are connected to each other to form a saturated or unsaturated group. It does not form a saturated fused ring. V ²¹ and V ²⁴ are preferably hydrogen atoms, and V ²² and V ²³ are each a hydrogen atom or an alkyl group (eg, methyl), an aryl group (eg, phenyl), an aromatic heterocyclic group (eg, 1-pyrrolyl), an alkoxy group. Group (eg, methoxy), alkylthio group (eg, methylthio), cyano group, halogen atom (eg, fluorine,
(Chlorine, bromine, iodine). V ²³ is more preferably a hydrogen atom, and V ²² is more preferably a halogen atom, particularly preferably a chlorine atom or a bromine atom.

The methine groups represented by L ²¹ , L ²² and L ²³ may be unsubstituted or substituted, and examples of the substituent include those represented by V. n ² is 0, 1,
It represents 2, 3 or 4, and when it is 2 or more, the methine group is repeated but need not be the same. Preferably 0,1,
2, 3, more preferably 0, 1, 2 and even more preferably 0 or 1. L ²¹ is preferably an unsubstituted methine group. When n ² is 1, L ²² is preferably a methine group substituted with an unsubstituted alkyl group, and L ²³ is preferably an unsubstituted methine group. It is preferable L ²² is especially methyl substituted methine group or an ethyl substituted methine group.

Examples of M ² include the respective ions described for M in the methine dye of the general formula (I).
Particularly, it is preferably a cation. Preferred cations are sodium, potassium, triethylammonium, pyridinium, N-ethylpyridinium. m ² represents a number of 0 or more necessary for neutralizing an intramolecular charge, and is 0 when an intramolecular salt is formed. Preferably it is 0, 1, 2, or 3.

Next, the cyanine dye represented by formula (II) used together with the methine dye of formula (I) will be described in detail.

In the general formula (II), the nitrogen-containing heterocyclic ring represented by Z ³¹ or Z ³² is a benzene ring, a cyclohexene ring,
A carbocycle such as a naphthalene ring may be fused, but a heterocycle is not fused. Z ³¹ and Z ³² are preferably a thiazoline ring, a thiazole ring, a benzothiazole ring, an oxazoline ring, an oxazole ring, a benzoxazole ring, a selenazoline ring, a selenazole ring, a benzoselenazole ring, a tellurazoline ring, a tellurazole ring, and a benzotellurazole ring. , 3,3-dialkylindolenine ring (eg, 3,3-dimethylindolenine), imidazoline ring, imidazole ring, benzimidazole ring, isoxazole ring, isothiazole ring, pyrazole ring, 2-pyridine ring, 4-pyridine ring , 2-quinoline ring, 4-quinoline ring, 1-isoquinoline ring, 3-isoquinoline ring, imidazo [4,5-b] quinoxaline ring, oxadiazole ring, thiadiazole ring, tetrazole ring, pyrimidine ring, and these rings Benzene ring, naphthalene ring, etc. Can be mentioned. More preferred are a benzoxazole ring, a benzothiazole ring, a benzimidazole ring and a quinoline ring, and still more preferred are a benzoxazole ring and a benzothiazole ring. These may be substituted by the respective substituents represented by V described above. As a specific example, see US Pat. No. 5,340,
No. 694, columns 23 to 24, the same as the examples of Z ₁₁ , Z ₁₂ , Z ₁₃ , Z ₁₄ and Z ₁₆ can be mentioned.

[0088] The alkyl group represented by R ^31, R ^32, aryl group, the heterocyclic group can be exemplified the groups described by R in methine dyes of the formula (I), R ^31,
R ³² is preferably an alkyl group is a group having an acid group or a dissociable proton was substituted, more preferably a carboxyl group, a sulfo group or -CONHSO _2, -, -
SO ₂ NHSO ₂ —, —CONHCO—, —SO ₂ NHC
A substituted alkyl group containing any one of O-, particularly preferably a 2-sulfoethyl group, a 3-sulfopropyl group, a 3-sulfobutyl group, a 4-sulfobutyl group, a carboxymethyl group or a methanesulfonylcarbamoylmethyl group. is there. More preferably, one of R ³¹ and R ³² is a 2-sulfoethyl group, a 3-sulfopropyl group,
A 3-sulfobutyl group or a 4-sulfobutyl group,
The other is a carboxymethyl group or a methanesulfonylcarbamoylmethyl group.

L ³¹ , L ³² , L ³³ , L ³⁴ , L ³⁵ , L ³⁶ , L
^The methine group represented by ³⁷ may be unsubstituted or substituted, and examples of the substituent include the respective substituents represented by V. L ³¹ , L ³² , L ³⁶ and L ³⁷ are preferably an unsubstituted methine group.

N ³ represents 0, 1, 2, 3 or 4;
In the above case, the methine group is repeated, but need not be the same. It is preferably 0, 1, 2, 3, more preferably 0, 1, 2, and even more preferably 0 or 1. p ³¹ and p ³² represent 0 or 1, and are preferably 0.

Examples of M ³ include each ion described for M in the methine dye of the general formula (I).
Particularly, it is preferably a cation. Preferred cations are sodium, potassium, triethylammonium, pyridinium, N-ethylpyridinium. m ³ represents a number of 0 or more necessary for neutralizing an intramolecular charge, and is 0 when an intramolecular salt is formed. Preferably it is 0, 1, 2, or 3.

The methine dye represented by the general formula (II) is more preferably represented by the general formula (IIa). In the general formula (IIa), X ⁴¹ and X ⁴² represent an oxygen atom, a sulfur atom,
Represents a selenium atom or NR ^23, oxygen atom, preferably a sulfur atom or NR ^43, it is preferable in particular oxygen atom or a sulfur atom.

R⁴¹, R⁴², R⁴³An alkyl group represented by
Examples of the aryl group and the heterocyclic group include the methyl group represented by the general formula (I).
Examples of the groups described for R in the dye include:
R⁴¹, R⁴²Preferably has an acid group or a dissociable proton.
Is a substituted alkyl group, more preferably
Carboxyl group, sulfo group, or -CONHSO _Two
-, -SO_TwoNHSO_Two-, -CONHCO-, -SO_Two
NHCO- is a substituted alkyl group containing any of
And particularly preferably a 2-sulfoethyl group, a 3-sulfoethyl group.
Propyl group, 3-sulfobutyl group, 4-sulfobutyl
Group, carboxymethyl group or methanesulfonylcarba
Moylmethyl group. More preferably, R⁴¹, R⁴²
Is a 2-sulfoethyl group, 3-sulfopro
Pill group, 3-sulfobutyl group or 4-sulfobutyl group
And the other is a carboxymethyl group or a methanes group.
It is a rufonylcarbamoylmethyl group. R⁴³Is preferably
Is an unsubstituted alkyl group, and is a methyl group or an ethyl group.
It is particularly preferred that there is.

V⁴¹, V⁴², V⁴³, V⁴⁴, V⁴⁵, V⁴⁶, V
⁴⁷, V⁴⁸Each of the substituents represented by V
Substituents, and two adjacent substituents are linked to each other
To form a saturated or unsaturated carbocyclic ring. That
Examples of such a saturated or unsaturated carbocycle include benzene
Zen ring, cyclohexene ring, naphthalene ring
However, it is preferable not to form a condensed ring.
V⁴¹, V⁴⁴, V⁴⁵, V⁴⁸Is preferably a hydrogen atom
, V⁴², V⁴³, V⁴⁶, V⁴⁷Is a hydrogen atom or alkyl
Groups (eg, methyl), aryl groups (eg, phenyl),
Aromatic heterocyclic group (eg, 1-pyrrolyl), alkoxy group
(Eg, methoxy), alkylthio group (eg, methylthio)
E), a cyano group, a halogen atom (for example, fluorine, chlorine,
Bromine, iodine). More preferably
V⁴³, V ⁴⁷Is a hydrogen atom and V⁴², V⁴⁶Is a halogen field
(Preferably chlorine or bromine).

The methine groups represented by L ⁴¹ , L ⁴² and L ⁴³ may be unsubstituted or substituted. Examples of the substituent include the substituents represented by V.

N ⁴ represents 0, 1, 2, 3 or 4;
In the above case, the methine group is repeated, but need not be the same. It is preferably 0, 1, 2, 3, more preferably 0, 1, 2, and even more preferably 0 or 1.

Examples of M ⁴ include each ion described for M in the methine dye of the general formula (I).
Particularly, it is preferably a cation. Preferred cations are sodium, potassium, triethylammonium, pyridinium, N-ethylpyridinium. m ⁴ represents a number of 0 or more necessary for neutralizing the intramolecular charge, and is 0 when an intramolecular salt is formed. Preferably it is 0, 1, 2, or 3.

The methine dye represented by the general formula (IIa) may further have the general formula (II) when used in a green-red sensitive emulsion.
I), when used in a blue-sensitive emulsion, it is preferably represented by the form (IV).

The dye represented by formula (III) will be described below in detail. X ⁵¹ and X in the general formula (III)
⁵² represents an oxygen atom or a sulfur atom. When used in a green-sensitive emulsion, X ⁵¹ is an oxygen atom or a sulfur atom, X ⁵² is an oxygen atom, and when used in a red-sensitive emulsion, X ⁵¹ is an oxygen atom or Preferably, the sulfur atom, X ⁵² is a sulfur atom.

R⁵¹, R⁵², R⁵³An alkyl group represented by
Examples of the aryl group and the heterocyclic group include the methyl group represented by the general formula (I).
Examples of the groups described for R in the dye include:
R⁵¹, R⁵²Preferably has an acid group or a dissociable proton.
Is a substituted alkyl group, more preferably
Carboxyl group, sulfo group, or -CONHSO _Two
-, -SO_TwoNHSO_Two-, -CONHCO-, -SO_Two
NHCO- is a substituted alkyl group containing any of
And particularly preferably a 2-sulfoethyl group, a 3-sulfoethyl group.
Propyl group, 3-sulfobutyl group, 4-sulfobutyl
Group, carboxymethyl group or methanesulfonylcarba
Moylmethyl group. More preferably, R⁵¹, R⁵²
Is a 2-sulfoethyl group, 3-sulfopro
Pill group, 3-sulfobutyl group or 4-sulfobutyl group
And the other is a carboxymethyl group or a methanes group.
It is a rufonylcarbamoylmethyl group. R⁵³Is preferably
Is an unsubstituted alkyl group, and is a methyl group or an ethyl group.
It is particularly preferred that there is.

The substituents represented by V ⁵¹ , V ⁵² , V ⁵³ , V ⁵⁴ , V ⁵⁵ , and V ⁵⁶ include the substituents represented by V, and two adjacent substituents are They do not combine to form a saturated or unsaturated fused ring. V ⁵¹ , V
⁵³ , V ⁵⁴ and V ⁵⁶ are preferably hydrogen atoms,
V ⁵² and V ⁵⁵ are an alkyl group (eg, methyl), an aryl group (eg, phenyl), an aromatic heterocyclic group (eg, 1-pyrrolyl), an alkoxy group (eg, methoxy), an alkylthio group (eg, methylthio), a cyano group, a halogen It is preferably an atom (eg, fluorine, chlorine, bromine, iodine), more preferably a halogen atom, and particularly preferably a chlorine atom or a bromine atom.

Examples of M ⁵ include the respective ions described for M in the methine dye of formula (I).
Particularly, it is preferably a cation. Preferred cations are sodium, potassium, triethylammonium, pyridinium, N-ethylpyridinium. m ⁵ represents a number of 0 or more necessary for neutralizing the intramolecular charge, and is 0 when an intramolecular salt is formed. Preferably it is 0, 1, 2, or 3.

Hereinafter, the dye represented by formula (IV) will be described in detail. In the general formula (IV), X ⁶¹ represents an oxygen atom or a sulfur atom, particularly preferably a sulfur atom.

[0104] The alkyl group represented by R ^61, R ^62, aryl group, the heterocyclic group can be exemplified the groups described by R in methine dyes of the formula (I), R ^61,
R ⁶² is preferably an alkyl group is a group having an acid group or a dissociable proton was substituted, more preferably a carboxyl group, a sulfo group or -CONHSO _2, -, -
SO ₂ NHSO ₂ —, —CONHCO—, —SO ₂ NHC
A substituted alkyl group containing any one of O-, particularly preferably a 2-sulfoethyl group, a 3-sulfopropyl group, a 3-sulfobutyl group, a 4-sulfobutyl group, a carboxymethyl group or a methanesulfonylcarbamoylmethyl group. is there. More preferably, one of R ⁶¹ and R ⁶² is a 2-sulfoethyl group, a 3-sulfopropyl group,
A 3-sulfobutyl group or a 4-sulfobutyl group,
The other is a carboxymethyl group or a methanesulfonylcarbamoylmethyl group.

The substituents represented by V ⁶¹ , V ⁶² , V ⁶³ , V ⁶⁴ , V ⁶⁵ , and V ⁶⁶ include the substituents represented by V, and two adjacent substituents are They do not combine to form a saturated or unsaturated fused ring. V ⁶¹ , V
⁶³ , V ⁶⁴ and V ⁶⁶ are preferably hydrogen atoms,
V ⁶² and V ⁶⁵ are an alkyl group (eg, methyl), an aryl group (eg, phenyl), an aromatic heterocyclic group (eg, 1-pyrrolyl), an alkoxy group (eg, methoxy), an alkylthio group (eg, methylthio), a cyano group, a halogen It is preferably an atom (eg, fluorine, chlorine, bromine, iodine), more preferably a halogen atom, and particularly preferably a chlorine atom or a bromine atom.

Examples of M ⁶ include the respective ions described for M in the methine dye of formula (I).
Particularly, it is preferably a cation. Preferred cations are sodium, potassium, triethylammonium, pyridinium, N-ethylpyridinium. m ⁶ represents a number of 0 or more necessary for neutralizing an intramolecular charge, and is 0 when an internal salt is formed. Preferably it is 0, 1, 2, or 3.

Preferred combinations of the compound of the general formula (I) and the compound of the general formula (II) which are preferable in the silver halide emulsion of the present invention are described below.

When used in the red-sensitive emulsion layer, the compound represented by the general formula
The compound of (II) is represented by the general formula (III),⁵¹And X⁵²
Are both sulfur atoms and R⁵¹And R⁵²Is a sulfoalkyl
Group, carboxyalkyl group or alkylsulfonylca
A rubamoylalkyl group;⁵³Is a methyl group or d
A tyl group;⁵¹, V⁵³, V⁵⁴, V⁵⁶Is a hydrogen atom
And V⁵², V⁵⁵Is an alkyl group (eg methyl), alcohol
Xy groups (eg, methoxy), alkylthio groups (eg,
Tylthio), a cyano group, a halogen atom (eg, fluorine,
Chlorine, bromine, iodine), more preferably a halogen atom,
Particularly preferred is a chlorine atom;^FiveIs organic or inorganic
Is a monovalent cation of^FiveIs 0 or 1
Is preferred. Compounds of general formula (I) in combination therewith
Is represented by the general formula (Ib),^{twenty one}And X^{twenty two}Is an oxygen source
And the other is a sulfur atom, Y^{twenty one}Is replaced by a halogen atom
A pyrrole, furan or thiophene ring
R^{twenty one}And R^{twenty two}Is a sulfoalkyl group, carboxyalkyl
Or alkylsulfonylcarbamoylalkyl group
And n^TwoIs 1 and L^{twenty one}, L^{twenty three}Is unsubstituted methine
Group, L^{twenty two}Is a methyl-substituted methine group or an ethyl-substituted methine
Group, V^{twenty one}, V^{twenty three}, V^{twenty four}Is a hydrogen atom and V ^{twenty two}Is
Alkyl group (for example, methyl) and alkoxy group (for example,
Toxyl), alkylthio groups (eg methylthio), shea
Group, halogen atom (for example, fluorine, chlorine, bromine, iodine
Element), more preferably a halogen atom,^TwoIs organic
Or an inorganic monovalent cation, m^TwoIs 0 or 1
It is preferred that

When used in a green-sensitive emulsion layer, the compound of the general formula (II) is represented by the general formula (III), and X ⁵¹ and X ⁵²
Are both oxygen atoms, R ⁵¹ and R ⁵² are a sulfoalkyl group, a carboxyalkyl group or an alkylsulfonylcarbamoylalkyl group, R ⁵³ is a methyl group or an ethyl group, and V ⁵¹ , V ⁵³ , V ⁵⁴ , V ⁵⁶ is a hydrogen atom; V ⁵² and V ⁵⁵ are an alkyl group (eg, methyl), an aryl group (eg, phenyl),
Thienyl), an alkoxy group (eg, methoxy), an alkylthio group (eg, methylthio), a cyano group, a halogen atom (eg, fluorine, chlorine, bromine, iodine), more preferably a halogen atom, and M ⁵ is an organic or inorganic monovalent. And m ⁵ is preferably 0 or 1. The compound of the general formula (I) combined therewith is represented by the general formula (Ib), X ²¹ and X ²² are both oxygen atoms, and Y ²¹ is a pyrrole ring, a furan ring or a furan ring substituted with a chlorine atom or a bromine atom. A thiophene ring, R ²¹ and R ²²
Is a sulfoalkyl group, a carboxyalkyl group or an alkylsulfonylcarbamoylalkyl group, n ² is 1, L ²¹ and L ²³ are an unsubstituted methine group, L ²² is a methyl-substituted methine group or an ethyl-substituted methine group, V ²¹ ,
V ²³ and V ²⁴ are hydrogen atoms, and V ²² is an alkyl group (eg, methyl), an aryl group (eg, phenyl), an aromatic heterocyclic group (eg, 2-thienyl), an alkoxy group (eg, methoxy), an alkylthio group ( For example, methylthio), a cyano group, a halogen atom (eg, fluorine, chlorine, bromine, iodine), more preferably a halogen atom, M ² is an organic or inorganic monovalent cation, and m ² is 0 or 1. Preferably, there is.

When used in the blue-sensitive emulsion layer, the compound represented by the general formula
A compound of the formula (II) represented by the general formula (IV)⁶¹Is sulfur field
Child and R⁶¹And R⁶²Is a sulfoalkyl group, carboxy
Alkyl group or alkylsulfonylcarbamoyl alcohol
A kill group, V⁶¹, V⁶³, V ⁶⁴, V⁶⁶Is a hydrogen atom
And V⁶², V⁶⁵Is an alkyl group (eg methyl), aryl
(For example, phenyl), an aromatic heterocyclic group (for example, 1-
Pyrrolyl), an alkoxy group (eg, methoxy),
Luthio group (eg methylthio), cyano group, halogen source
Child (eg fluorine, chlorine, bromine, iodine), more preferred
A halogen atom, particularly preferably a chlorine atom;
⁶Is an organic or inorganic monovalent cation, and m⁶Is 0
Or 1 is preferred. General combined with this
The compound of the formula (I) is represented by the general formula (Ib),^{twenty one}And X
^{twenty two}Are both sulfur atoms and Y^{twenty one}Is replaced by a halogen atom
A thiophene ring,^{twenty one}And R^{twenty two}Is a sulfoalk
Group, carboxyalkyl group or alkylsulfonyl
A carbamoylalkyl group, n^TwoIs 0 and L^{twenty one}
Is an unsubstituted methine group;^{twenty one}, V^{twenty three}, V^{twenty four}Is a hydrogen atom
And V^{twenty two}Is an alkyl group (eg methyl), alkoxy
Group (for example, methoxy), alkylthio group (for example, methyl
Ruthio), cyano group, halogen atom (eg, fluorine, salt
, Bromine, iodine), more preferably a halogen atom,
Is preferably a chlorine atom or a bromine atom;^TwoIs
Machine or inorganic monovalent cation, m^TwoIs 0 or
It is preferably 1.

Specific examples of the compounds of the general formula (I) of the present invention (including the compounds of the general formulas (Ia) and (Ib) as subordinate concepts) are shown below, but the present invention is limited thereby. Do not mean. Other than the following, Japanese Patent Application 2000-124
612 can be selected from the methine dyes S-1 to S-95.

[0112]

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The compounds of the general formula (II) of the present invention (general formulas (IIa), (III) and (III),
Specific examples of the compound (V)) are shown below, but the present invention is not limited thereto.

[0123]

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The general formulas (I) and (II) of the present invention
(Including subordinate compounds)
Hamer, Heterocyclic Compounds-Cyanine Dyes and R
Elated Compounds ", John Wiley & Sons, New York, London, 1964, DMSturmer," Heter
ocyclic Compounds-Special topics in heterocyclicch
emistry ", Chapter 18, Section 14, Chapters 482-515
Page, John Wiley & Sons, Inc.-New York, London,
1977, Rodd's Chemistry of Carbon Compoun
ds "2nd Ed. vol. IV, part B, 1977, Chapter 15,
369-422, Elsevier Science Publishing Co
It can be synthesized based on the method described in mpany Inc., New York, and the like.

The compound of the formula (I) and the compound of the formula (II) of the present invention may be used alone or in combination in the same emulsion. The addition ratio of the compound of the formula (I) and the compound of the formula (II) of the present invention in the same emulsion may be arbitrarily selected, and the preferred molar ratio varies depending on the use and purpose, but is preferably 1000/1. ~ 1
/ 1000, more preferably 100/1 to 1/1
00, more preferably 10/1 to 1/10.

The compound of the formula (I) and the compound of the formula (II) of the present invention may be used together with other sensitizing dyes other than the present invention in the same emulsion. Preferred examples of the dye used include a cyanine dye, a merocyanine dye, a rhodocyanine dye, a trinuclear merocyanine dye, a tetranuclear merocyanine dye, an allopolar dye, a hemicyanine dye, and a styryl dye. More preferred are cyanine dyes, merocyanine dyes and rhodacyanine dyes, and particularly preferred are cyanine dyes. For more information on these dyes, see
FM Hamer, Heterocyclic Compounds-Cyanine Dyes a
nd Related Compounds ", John Wiley & Sons, New York, London, 1964, DMSturmer," H
eterocyclic Compounds-Special topics in heterocycl
ic chemistry ", Chapter 18, Section 14, 482-51
It is described on page 5 and the like. Preferable general formulas of the dyes are described in U.S. Pat. No. 5,994,051, pp. 32 to 44, and 5,747,236, pp. 30 to 39, and specific examples. Sensitizing dyes. The general formulas of preferred cyanine dyes, merocyanine dyes and rhodacyanine dyes are described in US Pat.
No. 0,694, columns 21 to 22, (XI), (XII), (XII
I) (however, n ₁₂ , n ₁₅ , n ₁₇ , n ₁₈
Is not limited and is an integer of 0 or more (preferably 4 or less). ).

One of these sensitizing dyes that can be used in combination may be used, or two or more of them may be used.
Particularly, those having an effect of supersensitization are preferable, and typical examples thereof are U.S. Patent Nos. 2,688,545 and 2,972.
No. 7,229, No. 3,397,060, No. 3,5
No. 22,052, No. 3,527,641, No. 3,
Nos. 617,293, 3,628,964, 3,666,480, 3,672,898, 3,679,428, 3,303,377,
Nos. 3,769,301 and 3,814,609
No. 3,837,862, No. 4,026,70
7, UK Patent Nos. 1,344,281 and 1,50
7,803, JP-B-43-49336, 53-1
2375, JP-A-52-110618 and JP-A-52-1
No. 09925 and the like.

In addition to the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization.

Supersensitizers useful in spectral sensitization in the present invention (for example, pyrimidylamino compounds, triazinylamino compounds, azolium compounds, aminostyryl compounds, aromatic organic acid formaldehyde condensates, azaindene compounds, cadmium salts) , And combinations of supersensitizers and sensitizing dyes are described, for example, in US Pat.
No. 664, No. 3,615,613, No. 3,61
No. 5,632, No. 3,615,641, No. 4,5
Nos. 96,767, 4,945,038 and 4,
965,182, 4,965,182, 2,933,390, 3,635,721, 3,743,510, 617,295, No. 3,635,721 and the like, and the method described in the above-mentioned patent is also preferable as to its use.

Next, the silver halide photographic emulsion and the silver halide photographic light-sensitive material of the present invention will be described in detail. When to add the methine dyes of the general formulas (I) and (II) used in the present invention (the same applies to other sensitizing dyes and supersensitizers) to the silver halide emulsion of the present invention. May be during any step of emulsion preparation that has been found to be useful. For example, U.S. Pat. Nos. 2,735,766, 3,628,960, 4,183,756, 4,225,666,
As disclosed in JP-A-58-184142 and JP-A-60-196747, the timing before silver halide grain formation and / or before desalination, during and / or after desalination of silver halide grains, Until the start of ripening,
As disclosed in JP-A-8-113920, etc., it may be added at any time in the process immediately before or during the process of chemical ripening, or at any time before the application of the emulsion after the chemical ripening until coating. No. 4,225,6.
No. 66, JP-A-58-7629 and the like, the same compound may be used alone or in combination with a compound having a different structure, for example, during the particle forming step and during the chemical ripening step or after the completion of the chemical ripening step. Or may be added separately, such as before chemical ripening or during the process and after completion, or may be added by changing the type of compound and compound combination to be added separately. Good.

The methine dye of the present invention (and other sensitizers)
The same applies to dyes and supersensitizers).
Depending on the shape and size of the silver halide grains,
1 × 10^-6~ 8 × 10^-3In mole
Can be used. For example, silver halide grain size
Is 0.2 to 1.3 μm, 1 mole of silver halide
2 × 10^-6~ 3.5 × 10^-3Good molar addition
Best, 7.5 × 10 ^-6~ 1.5 × 10^-3Amount of mole added
Is more preferred.

The methine dye of the present invention (the same applies to other sensitizing dyes and supersensitizers) can be directly dispersed in an emulsion. Also, these are first suitable solvents,
For example, it can be dissolved in methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water, pyridine or a mixed solvent thereof and added to the emulsion in the form of a solution. At this time, additives such as a base, an acid and a surfactant can be coexisted. Also, ultrasonic waves can be used for dissolution. As a method for adding the compound, as described in US Pat. No. 3,469,987, the compound is dissolved in a volatile organic solvent, and the solution is dispersed in a hydrophilic colloid. As described in JP-B-46-24185, and a method of dispersing in a water-soluble solvent and adding this dispersion to the emulsion, described in U.S. Pat. No. 3,822,135. A method of dissolving a compound in a surfactant and adding the solution to an emulsion, and dissolving using a compound that causes a red shift as described in JP-A-51-74624, and dissolving the solution in the emulsion. Addition method, JP-A-50-80826
As described in (1), a method in which the compound is dissolved in an acid substantially free of water and the solution is added to the emulsion is used. In addition, US Pat.
No. 2,343, No. 3,342,605, No. 2,99
Nos. 6,287, 3,429,835 and the like can also be used.

As the organic solvent for dissolving the methine dye of the present invention, for example, methyl alcohol, ethyl alcohol,
Examples include n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, benzyl alcohol, fluorine alcohol, methyl cellosolve, acetone, pyridine, and a mixed solvent thereof.

When dissolving the methine dye of the present invention in water, the above-mentioned organic solvent, or a mixed solvent thereof, it is preferable to add a base. The base may be either an organic base or an inorganic base, and examples thereof include amine derivatives (eg, triethylamine, triethanolamine), pyridine derivatives, sodium hydroxide, potassium hydroxide, sodium acetate, and potassium acetate. As a preferable dissolving method, a method in which a dye is added to a mixed solvent of water and methanol, and further, triethylamine in an equimolar amount to the dye is added.

In the silver halide emulsion used in the present invention, the silver halide grains may be any of silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver iodochloride, silver chloroiodobromide and the like. For use in color photographic paper, for example, a silver chlorobromide emulsion is preferable for the purpose of speeding up and simplifying the processing, and 95 mol% or more of the silver chlorobromide emulsion is silver chloride. Certain silver chloride, silver chlorobromide, or silver chloroiodobromide can be preferably used. In particular, silver chlorobromide or silver chloride containing substantially no silver iodide can be preferably used to speed up the development processing time. Further, silver iodobromide emulsions are preferred for use in color photography films (negative and reversal), and silver iodobromide emulsions are preferably 95%.
Silver bromide, silver iodobromide, or silver chloroiodobromide in which at least mol% is silver bromide can be preferably used.

The average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined by the diameter of a circle equivalent to the projected area of the grain and the number average thereof is taken) is 0.1. ２2 μm is preferred. The particle size distribution is preferably a so-called monodisperse coefficient of variation (a standard deviation of the particle size distribution divided by the average particle size) of 20% or less, preferably 15% or less, more preferably 10% or less. At this time, for the purpose of obtaining a wide latitude, it is also preferable to use the above monodispersed emulsion by blending it in the same layer, or to perform multi-layer coating.

The silver halide grains contained in the photographic emulsion may have a regular crystal form such as cubic, octahedral or tetradecahedral, or irregular crystals such as spherical or tabular. It may have a shape or a mixture thereof. In the present invention, among these, 50% or more of the particles having the regular crystal form,
The content is preferably 70% or more, more preferably 90% or more.

The emulsion used in the present invention is described in P. Glafkides, "C
himie et Phisique Photographique "(Paul Montel, 1967), GFDuffin," Photographic Emuls
ion Chemistry "(Focal Press, 1966), V.
Making and coating Photographic by L. Zelikman et al
Emulsion "(Focal Press, 1964) and the like. That is, any method such as an acidic method, a neutral method, and an ammonia method may be used, and a method of reacting a soluble silver salt and a soluble halide salt includes a one-sided mixing method, a double-sided mixing method, and a combination thereof. A method may be used. A method of forming particles in an atmosphere containing excess silver ions (so-called reverse mixing method) can also be used. As one type of the double jet method, a method in which pAg in a liquid phase in which silver halide is formed is kept constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained.

In the emulsion used in the present invention, 50% or more, more preferably 70% or more, particularly preferably 80% or more of the total projected area of the silver halide grains in the emulsion is tabular grains having an aspect ratio of 2 or more. Preferably, the aspect ratio is 4 to 100, more preferably 6 to 80, and particularly preferably 8 to 60. For example, for color photographic paper applications, tabular grains of silver chlorobromide,
For color photography films, tabular grains of silver iodobromide are preferably used.

In general, tabular grains are tabular having two parallel planes, and thus "thickness" is represented by the distance between two parallel planes constituting the tabular grains. The diameter of a silver halide grain refers to the diameter of a circle having an area equal to the projected area of the grain in an electron micrograph, and the diameter / thickness ratio is called an aspect ratio.

The silver chlorobromide tabular grains used for color photographic paper will be described in detail. The silver chloride content is preferably 80 mol% or more, more preferably 95% or more. . Further, the silver chlorobromide particles preferably comprise a core portion and a shell portion (outermost layer) containing more iodide than the core portion. It is preferable that 90% or more of the core portion is silver chloride. The core portion may be composed of two or more portions having different halogen compositions. The shell part is preferably 50% or less of the total particle volume,
Particularly preferably, it is 0% or less. The silver iodide content of the shell part is preferably 0.5 to 13 mol%,
It is particularly preferred that it is 1 to 6 mol%. The content of silver iodide in all grains is preferably 0.1 to 5 mol%,
〜2 mol% or less is particularly preferred. The silver iodide content of the core is preferably at most 1 mol%, particularly preferably 0%. The silver bromide content may be different between the core part and the shell part. The silver bromide content is 0 based on the total silver.
-20 mol% is preferable, and 0.1-5 mol% is particularly preferable. The diameter of the high silver chloride tabular grains is preferably from 0.2 to
1.0 μm. The thickness is 0.2 μm or less, preferably 0.15 μm or less, and particularly preferably 0.1 μm or less. Further, the aspect ratio is preferably 3 to 20,
More preferably, it is 5 to 15. The particle size distribution of the high silver chloride tabular grains may be polydisperse or monodisperse, but is more preferably monodisperse. The dispersion coefficient of the particle size is preferably 5 to 25%, particularly preferably 5 to 20%. The dispersion coefficient of the particle thickness is also preferably 5 to 25%, particularly preferably 5 to 15%.

In the high silver chloride tabular grains used for color printing paper, a crystal habit controlling agent is used to form the {111} plane as the outer surface. The formation of tabular grains is achieved by generating two parallel twin planes, and the formation of twin planes depends on temperature, dispersion medium (gelatin), halogen concentration, etc., so these appropriate conditions are set. Must. When a crystal habit controlling agent is present during nucleation, the gelatin concentration is preferably 0.1 to 10%. The chloride concentration is 0.01 mol / liter or more, preferably 0.0
3 mol / liter or more. Japanese Patent Laid-Open No. 2000-2915 discloses a crystal habit controlling agent specifically used and a method for forming {111} high silver chloride tabular grains using the same.
No. 6 can be used.

The tabular grains may be tabular grains having {100} planes as main planes. The shape of the main plane is a right-angled parallelogram or a triangular to pentagonal shape in which one corner of the right-angled parallelogram is missing (a missing shape is a side having the corner as a vertex and the corner as the corner) A right-angled triangular portion formed by the above) or the missing portion exists in two or more and four or less.
To an octagonal shape. A method for forming tabular silver halide emulsion grains having a {100} major plane is described in, for example,
No. 301129, No. 6-347929, No. 9-340
No. 45, No. 9-96881, No. 8-122954,
No. 9-189977.

In silver iodobromide tabular grains used for color photography films, silver iodobromide, silver iodochloride, or chloroiodide containing 30 mol% or less of silver iodide as a halogen composition. Silver halide is preferred. Particularly preferred is silver iodobromide or silver iodochlorobromide containing 2 to 10 mol% of silver iodide. Although silver chloride may be contained, the silver chloride content is preferably 8 mol% or less, more preferably 3 mol% or less.
Mol% or less, or 0 mol%. The diameter of the silver iodobromide tabular grains is preferably 0.3 to 5.0 μm. The thickness of the tabular grains is preferably 0.05 to 0.5 μm. The aspect ratio of the tabular grains is preferably 4 to 50, more preferably 5 to 30, and still more preferably 6 to 25.

The silver halide emulsion used in the present invention is usually chemically sensitized. As a chemical sensitization method, a gold sensitization method using a so-called gold compound (for example, US Pat. No. 2,448,06)
0, 3,320,069), iridium, platinum,
Sensitization method using metals such as rhodium and palladium (for example, US Pat. Nos. 2,448,060 and 2,566,245)
No. 2,566,263), a sulfur sensitization method using a sulfur-containing compound (for example, US Pat. No. 2,222,264).
), A selenium sensitization using a selenium compound, a tellurium sensitization using a tellurium compound, or a reduction sensitization method using tin salts, thiourea dioxide, polyamine or the like (for example, U.S. Pat. Nos. 2,487,850 and 2,518). , 698 and 2,521, 925). These sensitization methods can be used alone or in combination.

The emulsion used in the present invention is preferably chemically sensitized with a selenium sensitizer. As the selenium sensitizer, a selenium compound disclosed in a conventionally known patent can be used. That is, usually, an unstable selenium compound and / or a non-unstable selenium compound is added,
It is used by stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain period of time. Examples of unstable selenium compounds include, for example, JP-B-44-15748 and JP-B-43-1.
3489, JP-A-4-25832, JP-A-4-10
It is preferable to use the compound described in No. 9240. Specific examples of unstable selenium sensitizers include isoselenocyanates (for example, aliphatic isoselenocyanates such as allyl isoselenocyanate), selenoureas, selenoketones, selenoamides, and selenocarboxylic acids (for example, Selenopropionic acid, 2-selenobutyric acid), selenoesters, diacylselenides (for example, bis (3
-Chloro-2,6-dimethoxybenzoyl) selenide), selenophosphates, phosphineselenides,
Colloidal metal selenium is mentioned.

The preferred types of unstable selenium compounds have been described above, but these are not limitative. Skilled artisans say that an unstable selenium compound as a sensitizer for a photographic emulsion is not very important as long as selenium is unstable, and the organic part of the selenium sensitizer molecule is not important. It is generally understood that selenium has no role except to carry it in an unstable form in the emulsion. In the present invention, an unstable selenium compound having such a broad concept is advantageously used.

The non-labile selenium compounds used in the present invention include JP-B-46-4553 and JP-B-52-34.
No. 492 and JP-B-52-34491 are used. Non-labile selenium compounds include, for example, selenous acid, potassium selenocyanide, selenazoles, quaternary salts of selenazoles, diaryl selenides, diaryl diselenides, dialkyl selenides, dialkyl diselenides, 2-selenazolidinediones, 2-selenooxazolidinethione and derivatives thereof.

Of these selenium compounds, those of the general formulas (VII) and (VIII) described in JP-A-11-15115 are preferably used. These selenium sensitizers are dissolved in water or an organic solvent such as methanol or ethanol alone or in a mixed solvent and added during chemical sensitization. Preferably, it is added before the start of chemical sensitization. The selenium sensitizer used is not limited to one type, and two or more of the above-mentioned selenium sensitizers can be used in combination. It is preferable to use a combination of an unstable selenium compound and a non-unstable selenium compound.
The amount of the selenium sensitizer to be added varies depending on the activity of the selenium sensitizer to be used, the type and size of silver halide, the ripening temperature and the time, and is preferably 1 × / mol of silver halide in the emulsion. It is at least 10 ^-8 mol. More preferably, it is 1 × 10 ^{−7 to} 5 × 10 ⁻⁵ mol. The temperature for chemical ripening when using a selenium sensitizer is preferably 45 ° C. or higher. More preferably, it is 50 to 80 ° C. pAg and pH are arbitrary. For example, the effects of the present invention can be obtained in a wide range of pH from 4 to 9.

The silver halide emulsion used in the present invention may contain various compounds or their precursors for the purpose of preventing fog during the production process, storage or photographic processing of the photographic material, or stabilizing photographic performance. Can be added. Specific examples of these compounds are disclosed in the above-mentioned JP-A-62-2.
Those described on page 39 to page 72 of JP-A-15272 are preferably used. Further EP0447647
5-arylamino-1,2,3,4-thiatriazole compounds (the aryl residue has at least one electron-withdrawing group) are also preferably used.

The silver halide emulsion prepared according to the present invention can be used for both color photographic materials and black-and-white photographic materials. Examples of the color photographic light-sensitive material include color photographic paper, color photographic film and color reversal film, and examples of the black-and-white photographic light-sensitive material include X-ray film, general photographic film, and print photographic material.

For the preparation of the photographic emulsion used in the present invention, column 63, line 36 to column 65, line 2 of JP-A-10-239789 can be applied. The types of photosensitive materials to which the present invention is applied, such as additives such as color couplers and photographic photosensitive material additives, and the processing of photosensitive materials, are described in JP-A-10-239789, column 65, line 3 to Column 73, line 13, etc. can be applied.

In the silver halide photographic light-sensitive material of the present invention,
Although the various additives described above are used, other various additives can be used according to the purpose. These additives are described in more detail in Research Disclosure Item 1
7643 (December, 1978), Item 18716 (November, 1979) and Item 308119 (December, 1989), and the corresponding portions are summarized in the table below.

Additive type RD17643 RD18716 RD308119 1 Chemical sensitizer page 23, page 648, right column, page 996 2 Sensitivity enhancer Same as above 3 Spectral sensitizer, page 23-24, page 648, right column-996 right-998 right Super strong Sensitizer 649 right column 4 Brightener 24 page 998 right 5 Antifoggant 24-25 page 649 right column 998 right to 1000 right and stabilizer 6 Light absorber, fill 25-26 page 649 right column 1003 left to 1003 right tar, UV absorber page 650 left column 7 Stain inhibitor 25 page right column 650 left to right column 1002 right 8 Dye image stabilizer 25 page 1002 right 9 Hardener 26 page 651 left column 1004 right 1005 left to 1004 right 11 Binders page 26 Same as above 1003 right to 1004 right 11 Plasticizers and lubricants 27 pages 650 pages right column 1006 left to 1006 right 12 Coating aids, pages 26 to 27 Same as above 1005 left to 1006 left Surfactant 13 Antistatic agent Page 27 Same as above 1006 right to 1007 left 14 Matting agent 1008 left to 1009 left

Emulsions used in the present invention, techniques such as layer arrangement which can be used for photographic light-sensitive materials using the emulsions, functional couplers such as silver halide emulsions, dye-forming couplers and DIR couplers, and various additives And development processing are described in EP 0 565 096 A1 (1.
(Published October 13, 993) and the patents cited therein. The following is a list of each item and the corresponding descriptions.

1. 1. Layer structure: page 61, lines 23 to 35, line 41 to page 62, line 14 2. Intermediate layer: page 61, lines 36 to 40 3. Multilayer effect imparting layer: page 62, lines 15 to 18 4. Silver halide composition: page 62, lines 21 to 25 5. Silver halide grain habit: page 62, lines 26 to 30 6. Silver halide grain size: page 62, lines 31 to 34 7. Emulsion production method: page 62, lines 35 to 40 8. Silver halide grain size distribution: page 62, lines 41 to 42 Tabular grains: page 62, lines 43 to 46 10. 10. Internal structure of particle: page 62, lines 47 to 53 11. Emulsion latent image formation type: page 62, line 54 to page 63, line 5 12. Physical ripening and chemical sensitization of emulsion: page 63, lines 6-9. 13. Mixed use of emulsion: page 63, lines 10-13. 14. Fogged emulsion: page 63, lines 14 to 31 Non-light-sensitive emulsion: page 63, lines 32 to 43 Silver coating amount: 63 pages, 49-50 lines

17. Formaldehyde scavenger: page 64, lines 54 to 57 18. Mercapto antifoggant: page 65, lines 1 and 2 19. Release agent such as fogging agent: page 65, lines 3-7 20. Dye: page 65, lines 7 to 10 21. General color couplers: page 65, lines 11 to 13 Yellow, magenta and cyan couplers: page 65, lines 14-25 23. Polymer coupler: page 65, lines 26-28 24. Diffusible dye-forming coupler: page 65, lines 29-31 25. Colored coupler: page 65, lines 32-38 26. Functional couplers in general: p. 65, lines 39-44 27. Bleach accelerator releasing coupler: page 65, lines 45-48 28. Development accelerator releasing coupler: page 65, lines 49 to 53 29. Other DIR couplers: page 65, line 54 to page 66, line 4 Coupler dispersion method: page 66, lines 5-28

31. Preservatives / fungicides: page 66, lines 29-33 32. Type of photosensitive material: page 66, lines 34-36 33. Photosensitive layer thickness and swelling speed: page 66, line 40 to page 67, line 1 34. Back layer: page 67, lines 3-8 35. Overall development processing: page 67, lines 9 to 11 Developer and developer: page 67, lines 12-30 37. Developer additive: page 67, lines 31 to 44 38. Inversion processing: page 67, lines 45 to 56 39. Processing solution opening ratio: page 67, line 57 to page 68, line 12 Developing time: page 68, lines 13 to 15 41. Bleaching / fixing / bleaching / fixing: page 68, line 16 to page 69, line 31 Automatic developing machine: page 69, lines 32 to 40 43. Rinsing, rinsing, stabilization: page 69, line 41 to page 70, line 18 Processing solution replenishment and reuse: page 70, lines 19 to 23 45. Built-in photosensitive material for developer: Page 70, lines 24 to 33 46. Developing temperature: page 70, lines 34-38 47. Use for film with lens: 70 pages 39-41

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EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples, but it should not be construed that the invention is limited thereto.

Example 1 (Preparation of {111} high silver chloride tabular grains) 1.2 liters of water
2.0 g NaCl and inert gelatin in a torr.
Add 4 g and stir into a container maintained at 33 ° C. while stirring.
NO_Three60cc aqueous solution (AgNO_Three 9g) and NaCl aqueous solution
60cc of liquid (3.2g of NaCl) by double jet method
For 1 minute. 1 minute after completion of addition
1 mmol was added. After another minute, NaCl
3.0 g were added. Over the next 25 minutes
The temperature was raised to 60 ° C. After aging at 60 ° C for 16 minutes, 10
% Phthalated gelatin aqueous solution and 290 g of crystal habit modifier-1
0.8 mmol was added. After this, AgNO _ThreeAqueous solution 7
54cc (AgNO_Three113 g) and an aqueous NaCl solution 76
8cc (41.3g of NaCl) accelerated over 28 minutes
Was added at the indicated flow rate. During this time, from 21 minutes to 28 minutes
KI (the amount added is such that the iodine content in the outermost layer is 0.5%).
11 mg of yellow blood salt and iridium hexachloride
1.5 × 10^-80.25 M NaCl aqueous solution containing
30 cc was added. After completion of addition, 1% potassium thiocyanate
And sensitizing dyes described in Table 1 were added.
Was. Thereafter, the temperature was raised to 75 ° C., and stirring was continued for 10 minutes.
After lowering the temperature to 40 ° C.,
The desalting process was performed by the flocculation method. Desalination
Then, add 67g of gelatin and 80cc of phenol (5%)
And 150 cc of distilled water. Sodium hydroxide
And AgNO_ThreePH 6.2 and pAg 7.5 with solution
Was. In this way, 96% of the total projected area has an average sphere equivalent diameter of 0.
65 μm, average equivalent circle diameter 1.19 μm, average thickness
0.13 μm tabular grains with an average aspect ratio of 9.1
The emulsions 101 to 129 were obtained. (Chemical sensitization) Emulsions 101 to 129 were prepared at 60 ° C.
Sodium thiosulfonate, 1- (5-methylureido)
Phenyl) -5-mercaptotetrazole, selenium compound
Product-1, sodium thiosulfate and chloroauric acid.
Appropriate chemical sensitization.

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(Preparation of Coated Sample) A corona discharge treatment was applied to the surface of a support obtained by coating both sides of a paper with a polyethylene resin, and then a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided. Samples 101 to 129 of silver halide color photographic light-sensitive materials having the following layer constitutions were prepared by sequentially coating the photographic constitutions of the layers to the seventh layer. After dissolving emulsions 101 to 129 at 40 ° C, 12
Sample 1 which was aged under stirring for a period of time and then applied similarly
01A to 129A were also created. The coating solution for each photographic constituent layer was prepared as follows.

Preparation of Coating Solution A coupler, a color image stabilizer and an ultraviolet absorber were dissolved in a solvent and ethyl acetate, and this solution was added to a 10% by weight containing a surfactant.
The mixture was emulsified and dispersed in an aqueous gelatin solution with a high-speed stirring emulsifier (dissolver), and water was added to prepare an emulsified dispersion. The emulsified dispersion and the high silver chloride emulsion were mixed and dissolved to prepare a coating solution having the following composition.

As the gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. Ab-1, Ab-2 and Ab-3 were added to each layer.
Are 15.0 mg / m ² and 60.0 mg / m, respectively.
was added such that the m ² and 5.0 mg / m ^2.

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The high silver chloride emulsion used in each photosensitive emulsion layer is as follows. (Blue photosensitive emulsion layer) The above-mentioned silver chloride tabular emulsion was used. (Green photosensitive emulsion layer) Silver chlorobromide emulsion (cubic, 1: 3 mixture of large size emulsion having an average grain size of 0.45 μm and small size emulsion of 0.35 μm, silver molar ratio) Coefficient of variation of grain size The sensitizing dye III-19 was added to the emulsions of each size in which 0.4 mol% of silver bromide was locally contained on a part of the surface of the silver chloride-based grains. Silver one
3.0 × for large size emulsions per mole
^10-4 moles, 3.6 × each for small size emulsions
10 ^-4 mol was added. In addition, II-18 was replaced with silver halide 1
4.0 × per mole for large size emulsions
10 ^-5 moles, 2.8 × each for small size emulsions
10 ^-4 mol was added.

(Red-sensitive emulsion layer) Silver chlorobromide emulsion (cubic, 1: 4 mixture of large-size emulsion A having an average grain size of 0.50 μm and small-size emulsion B having an average grain size of 0.41 μm (silver molar ratio)). The coefficient of variation of the particle size is 0.09 and 0.11.
In each emulsion, 0.8 mol% of silver bromide was locally contained on a part of the surface of the silver chloride-based grains. II-19 and II-10 were added per mol of silver halide at 6.0 × 10 ^-5 mol for large-size emulsion and 9.0 × 10 ^-5 mol for small-size emulsion, respectively. did.

Further, the following compound I was added in an amount of 2.6 × 10 ⁻³ mol per mol of silver halide.

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In addition, 1- (3-methylureidophenyl) -5-mercaptotetrazole was added to the blue-sensitive, green-sensitive and red-sensitive emulsion layers in an amount of 3.3 × 10 ^-4 mol per mol of silver halide. , 1.0 × 10 ^-3 mol and 5.9 × 10 ^-4 mol. Further, the second layer, the fourth layer, the sixth layer, and the seventh layer each have a concentration of 0.2 mg / m2.
² , 0.2 mg / m ² , 0.6 mg / m ² and 0.1 m
g / m ² . Also, 0.05 g / m ^{2 of a} copolymer of methacrylic acid and butyl acrylate (weight ratio 1: 1, average molecular weight 200000 to 400,000) was added to the red-sensitive emulsion layer. Further, disodium catechol-3,5-disulfonate was added to the second, fourth and sixth layers at 6 mg / m ² , 6 mg / m ² and 18 m, respectively.
g / m ² . To prevent irradiation, the following dyes were added to the emulsion layer (the amount in parentheses indicates the coating amount).

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(Layer Structure) The layer structure is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver. Support: polyethylene resin laminated paper [A white pigment (TiO ₂ ; content: 16% by weight, ZnO: content: 4% by weight) and a fluorescent whitening agent (4,4′-bis (5 -Methylbenzoxazolyl) stilbene at 13 mg / m ² ) and bluish dye (ultramarine) at 96 mg
mg / m ² ]

First layer (blue-sensitive emulsion layer) Emulsion 0.24 Gelatin 1.25 Yellow coupler (ExY) 0.57 Color image stabilizer (Cpd-1) 0.07 Color image stabilizer (Cpd-2) 0 .04 Color image stabilizer (Cpd-3) 0.07 Color image stabilizer (Cpd-4) 0.02 Solvent (Solv-1) 0.21

Second layer (color mixture prevention layer) Gelatin 0.60 Color mixture prevention agent (Mid-1) 0.10 Color mixture prevention agent (Mid-2) 0.18 Color mixture prevention agent (Mid-3) 0.02 UV absorption Agent (UV-C) 0.05 Solvent (Solv-5) 0.11

Third layer (green-sensitive emulsion layer) Emulsion 0.14 Gelatin 0.73 Magenta coupler (ExM) 0.15 Ultraviolet absorber (UV-A) 0.05 Color image stabilizer (Cpd-2) 02 Color mixture inhibitor (Cpd-3) 0.008 Color image stabilizer (Cpd-4) 0.08 Color image stabilizer (Cpd-5) 0.02 Color image stabilizer (Cpd-6) 0.009 Color image Stabilizer (Cpd-7) 0.0001 Solvent (Solv-3) 0.06 Solvent (Solv-4) 0.11 Solvent (Solv-5) 0.06

Fourth Layer (Color Mixing Prevention Layer) Gelatin 0.48 Color Mixture Prevention Agent (Mid-4) 0.07 Color Mixture Prevention Agent (Mid-2) 0.006 Color Mixture Prevention Agent (Mid-3) 0.006 Ultraviolet Absorption Agent (UV-C) 0.04 Solvent (Solv-5) 0.09

Fifth layer (red-sensitive emulsion layer) Emulsion 0.12 Gelatin 0.59 Cyan coupler (ExCA) 0.13 Cyan coupler (ExCB) 0.03 Color mixture inhibitor (Mid-3) 01 Color image stabilizer (Cpd-5) 0.04 Color image stabilizer (Cpd-8) 0.19 Color image stabilizer (Cpd-9) 0.04 Solvent (Solv-5) 0.09

Sixth layer (ultraviolet absorbing layer) Gelatin 0.32 Ultraviolet absorbing agent (UV-C) 0.42 Solvent (Solv-7) 0.08

Seventh layer (protective layer) Gelatin 0.70 Acrylic modified polymer of polyvinyl alcohol (degree of modification 17%) 0.04 Liquid paraffin 0.01 Surfactant (Cpd-13) 0.01 Polydimethylsiloxane 0 .01 silicon dioxide 0.003

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As described above, 1 to 1
29 and 101A-129A were made. (Exposure) Using the exposure apparatus described below, B, G, and R laser beams of three colors were used to expose three color separation gradations. At that time, the laser output was corrected for each sample so as to obtain the optimum improvement.

(Exposure apparatus) The light source is a semiconductor laser GaAlAs
LiNbO3 with inverted domain structure using YAG solid laser (oscillation wavelength 946 nm) with excitation light source (oscillation wavelength 808.5 nm)
473 nm wavelength-converted by the SHG crystal of the laser and a YVO4 solid-state laser (oscillation wavelength of 1064 nm) using the semiconductor laser GaAlAs (oscillation wavelength of 808.5 nm) as the excitation light source were wavelength-converted by the LiNbO3 SHG crystal having the inversion domain structure. The 532 nm taken out and AlGaInP (oscillation wavelength 680 nm: type No.LN9R20 manufactured by Matsushita Electric Industrial Co., Ltd.) were used. The laser light of each of the three colors was intensity-modulated by the AOM, moved in a direction perpendicular to the scanning direction by a polygon mirror, and allowed to be sequentially scanned and exposed on color photographic paper. Fluctuations in light intensity due to the temperature of the semiconductor laser are suppressed by using a Peltier element to keep the temperature constant. This scanning exposure is 600d
pi, and in the light beam diameter measurement using a light beam diameter measurement device [1180GP / manufactured by Beam Scan (USA)], B,
Both G and R were 65 μm (a circular beam having a difference of 1% or less in diameter in the main scanning direction / diameter in the sub-scanning direction).

(Development treatment: dry to dry 55 seconds) The above sample was subjected to color development treatment by the following processing steps and processing solutions. Processing process Temperature Time Replenisher ^* Tank capacity Color development 45 ° C 15 seconds 35ml 2L Bleaching and fixing 40 ° C 15 seconds 38ml 1L Rinse 40 ° C 5 seconds ――― 1L Rinse 40 ° C 5 seconds ――― 1L Rinse 40 ° C 5 seconds 90ml 1L drying 80 ° C. 10 seconds --- --- (as a tank countercurrent system to rinse →) * replenishment rate per photosensitive material 1 m ²

In the above treatment, the rinse water was pumped to the reverse osmosis membrane, the permeated water was supplied to the rinse, and the concentrated water that did not pass through the reverse osmosis membrane was returned to the rinse for use. In addition,
In order to reduce the crossover time between the rinses, a blade was installed between the tanks, and the photosensitive material was passed between them. In each step, a circulating treatment liquid was sprayed using a spraying device described in JP-A-8-314088, with the spraying amount set at 4 to 6 L / min per tank.

The composition of each processing solution is as follows. Color developer Tank solution Replenisher Water 700ml 700ml Sodium triisopropylnaphthalene (β) sulfonate 0.1g 0.1g Ethylenediaminetetraacetic acid 3.0g 3.0g 1,2-Dihydroxybenzene-4,6-disulfonate disodium salt 0.5 g 0.5 g triethanolamine 12.0 g 12.0 g potassium chloride 15.8 g --- potassium bromide 0.04 g --- potassium carbonate 27.0 g 27.0 g sodium sulfite 0.1 g 0.1 g disodium N, N-bis (sulfonatoethyl) hydroxylamine 18.0 g 18.0 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 8.0 g 23.0 g sodium Bis (2,4-disulfonatoethyl-1,3,5-tria Emissions -6 - yl) diaminostilbene-2,2-disulfonate 5.0 g 6.0 g Water to make 1000ml 1000ml pH (25 ℃) 10.35 12.80

The bleach-fix solution was prepared by mixing two replenishers as follows. Bleach-fix solution Tank solution Replenishment amount (38 ml per 1 m ^{2 in the following} amount) First replenisher 260 ml 18 ml Second replenisher 290 ml 20 ml Add water 1000 ml pH (25 ° C) 5.0

The composition of the first and second replenishers is as follows. (First replenisher) Water 150 ml Ethylene bisguanidine nitrate 30 g Ammonium sulfite / monohydrate 226 g Ethylenediaminetetraacetic acid 7.5 g Triazinylaminostilbene-based fluorescent whitening agent 1.0 g (Showa Chemical's Hakkol FWA-SF) bromide Ammonium 30 g Ammonium thiosulfate (700 g / L) 340 ml Add water 1000 ml pH (25 ° C.) 5.82 (second replenisher) Water 140 ml Ethylenediaminetetraacetic acid 11.0 g Ammonium iron (III) ethylenediaminetetraacetate 384 g Acetic acid (50% ) 230ml Add water 1000ml pH (25 ° C) 3.35 (Rinse solution) Deionized water (Ca, Mg 3ppm or less each)

(Comparison Processing) For comparison, a CP45-X processing (dry to d) manufactured by Fuji Photo Film Co., Ltd.
ry 130 seconds). Each step of color development and bleach-fixing = 45 seconds, each step of rinsing and rinsing = 20 seconds

The color density of the processed color sample was measured for reflection density using a TCD type density measuring device manufactured by Fuji Photo Film Co., Ltd. The sensitivity was determined from the exposure required to give a color density 1.0 higher than the fog density. The blue sensitivity was expressed as a relative value with the sensitivity of the sample 101 processed for 130 seconds as 100. Fog consists of color development of the coupler due to development of the unexposed area and residual color of the sensitizing dye. Table 1 shows the measurement results.

[0212]

[Table 1]

As can be seen from the results shown in Table 1, the compounds of the present invention represented by the general formula (I) and the compounds represented by the general formula (II) (in this case, the compounds represented by the general formula (IV) of the subordinate concept) (Including the compounds represented by the above formulas) alone, not only does not provide sufficient sensitivity, but also after the dissolution of the emulsion, the silver halide grains agglomerate to cause a decrease in sensitivity and an increase in fog. This problem was not solved by the combined use of the compounds (I) and the combined use of the compounds (II). Further, in the case of using the compound (II) alone or in combination of two kinds of the compound (II), fog (due to the residual color of the sensitizing dye) deteriorated, and the tendency was remarkable in rapid processing. Compared with these, the combined use of the compound of the general formula (I) and the compound of the general formula (II) according to the present invention significantly improves the sensitivity, suppresses the deterioration of the photographic performance after dissolution aging, and improves the photographic processing. Subsequent reduction of residual color can be achieved at the same time. As described above, only when the compound of the general formula (I) and the compound of the general formula (II) of the present invention are used at the same time, the specific sensitivity is high without deteriorating the residual color. In this case, it was found that an emulsion having reduced sensitivity and increased fog could be obtained.

Example 2 (Preparation of Sample 201) A multilayer color photosensitive material was prepared according to the method of preparing Sample 101 in Example 1 described in JP-A-11-119365, to obtain Sample 201. Sample 2
Table 2 shows the photosensitive emulsion used in No. 01.

[0215]

[Table 2]

Note 1) Each of the above emulsions is a silver iodobromide emulsion chemically sensitized with gold, sulfur and selenium. Note 2) In each of the above emulsions, a sensitizing dye was added before chemical sensitization. Note 3) The emulsions described above include compounds F-5, F-7, F-8, F-9, F-9 described in JP-A-11-119365.
10, F-11, F-12, F-13, and F-14 are appropriately added. Note 4) Emulsions A, B, I and J are triple-structure tabular grains having a (100) major plane and the other (111) major plane. Note 5) Emulsions A, B, E, F, I and P are emulsions whose internal sensitivity is higher than surface sensitivity. Note 6) Emulsions E, I and P are grains obtained by epitaxially growing silver chloride after chemical sensitization. Note 7) 50 per grain for grains other than emulsions A, E and F
More than one dislocation is a particle observed by a transmission electron microscope.

(Preparation and Evaluation of Samples 200 and 202 to 211) The sensitizing dyes III-15 and II-21 of Emulsions A to E used in Sample 201 were replaced by equimolar amounts as shown in Table 3 to obtain Samples 202 to 202-2. 211, and a dye blank sample 200 was prepared by removing the dye. In the table, 202, 2
No dye corresponding to II-21 was added to 03 and 210. The thus-obtained sample piece was exposed to white light through a gray wedge at an exposure time of 1/100 second and an exposure amount of 20 CMS, and then processed in the following processing steps to perform sensitometry. The residual color was evaluated by subtracting the cyan stain concentration of the dye blank sample 200 from the stain cyan concentration of the treated sample. The stain concentration was measured with a concentration meter, status A manufactured by X-RITE. Further, each sample was exposed through a pattern for measuring the RMS value using a halogen lamp having a color temperature of 3200 ° K as a light source, and the sample was subjected to the following processing, measured using a microdensitometer (measurement aperture diameter: 48 μm), and the RMS value was measured. I asked.

(Processing) Processing Step Time Temperature Tank capacity Replenishment amount First development 6 minutes 38 ° C 12L 2200ml / m ² First water wash 2 minutes 38 ° C 4L 7500ml / m ² Inversion 2 minutes 38 ° C 4L 1100ml / m ² color developing 6 minutes 38 ℃ 12L 2200ml / m ² before bleaching 2 min 38 ℃ 4L 1100ml / m ² bleaching 6 min 38 ℃ 2L 220ml / m ² Fixing 4 min 38 ℃ 8L 1100ml / m ² second water washing 2 min 38 ℃ 8L 7500ml / m ² Final rinse 1 minute 25 ℃ 2L 1100ml / m ²

The composition of each processing solution is described in JP-A-11-11936.
It is the same as that of Example 1 described in the specification of No. 5.

Table 3 below shows the evaluation results of sensitometry, residual color and granularity. The red relative sensitivity was compared based on the relative exposure from the minimum density to the density increase of 1.0 (sample 20).
The sensitivity of 2 is 100). The RMS value is shown as a relative value when the value of the sample 202 is 100 with respect to the value of the density 0.7 of the cyan image (the smaller the value, the better the graininess).

[0221]

[Table 3]

As is clear from the results shown in Table 3, the compounds of the present invention represented by the general formula (I) and the compounds represented by the general formula (II) (in this case, the general formula (III) of the lower concept) ) Alone, sufficient sensitivity cannot be obtained, and the deterioration of graininess presumably caused by aggregation of silver halide grains is observed. When the compounds of (I) and the compounds of (II) are used in combination, the granularity is slightly improved, but the sensitivity is not improved, and (II)
When the compounds were used together, the residual color also deteriorated. Compared with these, it was confirmed that the combination of the compound of the general formula (I) and the compound of the general formula (II) according to the present invention significantly improved the sensitivity and the granularity. Also, there was almost no deterioration of the residual color. As described above, only when the compound of the general formula (I) and the compound of the general formula (II) of the present invention are used at the same time, specifically, it is possible to achieve both the sensitivity and the granularity without deteriorating the residual color. It has been found that a realized emulsion can be obtained.

Example 3 (Preparation of Sample 301) A multilayer color photosensitive material was prepared according to the method of preparing Sample 101 in Example 1 described in JP-A-11-305396, to obtain Sample 301. However, Example 1 described in JP-A-11-305396 was used.
The sensitizing dye therein is read as follows in the present invention. ExS-1 → Dye II-21 ExS-2 → Dye II-22 ExS-3 → Dye III-15 ExS-4 → Dye III-10 ExS-5 → Dye II-30 ExS-6 → Dye III-9 ExS- 7 → Dye II-16 ExS-8 → Dye III-8 ExS-9 → Dye IV-7 ExS-10 → Dye II-31

The AgI content, grain size, surface iodine content and the like of the emulsion used are shown in Table 4 below.

[0225]

[Table 4]

In Table 4, (1) Emulsions L to O were subjected to reduction sensitization during the preparation of grains using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-191938. (2) Emulsions A to O were subjected to gold sensitization, sulfur sensitization and selenium sensitization in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate according to the examples of JP-A-3-237450. Have been. (3) For preparing tabular grains, low molecular weight gelatin is used according to the examples of JP-A-1-158426. (4) Dislocation lines described in JP-A-3-237450 are observed in the tabular grains using a high-pressure electron microscope.

(Preparation of Samples 302 to 304) Sample 301
Samples 302 to 304 were prepared in the same manner except that the sensitizing dyes of the 10th and 11th layers were changed to the sensitizing dyes in Table 5 below.

(Preparation of Samples 305 to 308) After preparing the coating solutions for the tenth and eleventh layers used in Samples 301 to 304 described above, the samples were coated for 12 hours with stirring for 12 hours. 308 was created.

The samples described above were evaluated for sensitivity, fog, and the effects of emulsion dissolution over time by the following methods. The above sample was exposed to sensitometry for 1/100 second through a continuous wedge and a gelatin filter SC-50 manufactured by Fuji Photo Film Co., Ltd. at a color temperature of 4800 ° K., and subjected to the following color development processing.

(Processing method) Step Processing time Processing temperature Color development 3 minutes 15 seconds 38 ° C. Bleaching 3 minutes 00 seconds 38 ° C. Water washing 30 seconds 24 ° C. Fixing 3 minutes 00 seconds 38 ° C. Water washing (1) 30 seconds 24 ° C. Washing with water (2) 30 seconds 24 ° C Stability 30 seconds 38 ° C Drying 4 minutes 20 seconds 55 ° C

The composition of each processing solution is described in JP-A-11-30539.
It is the same as that of Example 1 described in the specification of No. 6.

Samples 301 to 308 subjected to the above development processing
Was measured for magenta density. As for the sensitivity, the relative value of the reciprocal of the exposure amount required for increasing the optical density by 0.2 from the fog was set to 100 in the case of the sample 301.
Fog consists of color development of the coupler in the unexposed area and residual color of the sensitizing dye. The results are shown in Table 5 below.

[0233]

[Table 5]

As is clear from the results in Table 5, the compound represented by the general formula (I) of the present invention and the compound represented by the general formula (II) (in this case, the general formula (III ), It is possible to obtain a silver halide photographic light-sensitive material having less residual color and high sensitivity, unlike the comparative example combining only the compound (II). I understand. Further, the silver halide photographic light-sensitive material of the present invention can maintain high sensitivity and low fog even after the dissolution of the emulsion has elapsed, which is considered to be caused by suppression of aggregation of silver halide grains. As described above, only when the compound of the general formula (I) and the compound of the general formula (II) of the present invention are used at the same time, specifically, with high sensitivity and little residual color,
It has been found that even when the emulsion is dissolved over time, an emulsion having less decrease in sensitivity and little increase in fog can be obtained.

Example 4 (Preparation of Silver Bromide Octahedral Emulsion (Emulsion A) and Silver Bromide Tabular Emulsion (Emulsion B and Emulsion C))
0 ml, 25 g of deionized bone gelatin, 50% N
15 ml of an H ₄ NO ₃ aqueous solution and 7.5 ml of a 25% NH ₃ aqueous solution were added, and the mixture was kept at 50 ° C., stirred well, and 750 ml of a 1N AgNO ₃ aqueous solution and 1 mol / L of KBr were added.
The aqueous solution was added in 50 minutes, and the silver potential during the reaction was set to -40 mV.
Kept. The obtained silver bromide particles were octahedral and had a sphere equivalent diameter of 0.846 ± 0.036 μm. The temperature of the emulsion was lowered, a copolymer of isobutene and monosodium maleate was added as a flocculant, and the emulsion was washed by settling and desalted. Then 95 g of deionized bone gelatin and 430 water
pH 6.5 at 50 ° C., and pAg8.
After adjustment to 3, potassium thiocyanate, chloroauric acid and sodium thiosulfate were added to obtain the optimum sensitivity.
Aged at 5 ° C. for 50 minutes. This emulsion was designated as emulsion A.

6.4 g of KBr and 6.2 g of low-molecular-weight gelatin having an average molecular weight of 15,000 or less are dissolved in 1.2 liters of water, and 8.1 ml of a 16.4% aqueous solution of AgNO ₃ and 23 7.2 ml of a 0.5% aqueous KBr solution
Was added by the double jet method over 10 seconds. Next, an aqueous solution of 11.7% gelatin was further added, the temperature was raised to 75 ° C., and the mixture was aged for 40 minutes. Then, 32.2% of AgNO ₃ was added.
370 ml of an aqueous solution and a 20% aqueous KBr solution were added over 10 minutes while keeping the silver potential at -20 mV, and 1
After physical ripening for minutes, the temperature was lowered to 35 ° C. Thus, a monodispersed pure silver bromide tabular emulsion (specific gravity: 1.15) having an average projected area diameter of 2.32 μm, a thickness of 0.09 μm, and a diameter variation coefficient of 15.1% was obtained. Thereafter, soluble salts were removed by the coagulation sedimentation method. The temperature was again maintained at 40 ° C.
6 g, 10 ml of a 1 mol / L aqueous solution of sodium hydroxide, 167 ml of water, and 1.66 ml of 35% phenoxyethanol were added to adjust the pAg to 8.3 and the pH to 6.20. This emulsion was ripened at 55 ° C. for 50 minutes by adding potassium thiocyanate, chloroauric acid and sodium thiosulfate to obtain the optimum sensitivity. This emulsion was designated as emulsion B. An emulsion chemically sensitized with potassium thiocyanate, chloroauric acid, pentafluorophenyl-diphenylphosphine selenide and sodium thiosulfate instead of potassium thiocyanate, chloroauric acid and sodium thiosulfate was used as emulsion C.

The emulsion obtained as described above was added to the dyes shown in Table 6 while keeping the emulsion at 50 ° C., and the mixture was stirred for 30 minutes, and further stirred at 60 ° C. for 60 minutes.

A gelatin hardener and a coating aid were added to the obtained emulsion, and the emulsion was coated simultaneously with a gelatin protective layer on a cellulose acetate film support so that the coated silver amount was 3.0 g silver / m ^2. By coating, samples 401 to 409 were obtained. The obtained film was placed in a tungsten bulb (color temperature 2).
854K) for 1 second through a continuous wedge color filter. Fuji gelatin filter SC-46 for minus blue exposure that excites the dye side as a color filter
The light having a wavelength of 460 nm or less was blocked using (manufactured by Fujifilm Corporation) and the sample was irradiated. The exposed sample was developed at 20 ° C. for 10 minutes using the following surface developer MAA-1. Next, the following fixing was performed, followed by washing with water and drying.

Surface developer MAA-1 Metol 2.5 g L-ascorbic acid 10 g Nabox (Fuji Film Co., Ltd.) 35 g Potassium bromide 1 g Water was added to add 1 liter pH 9.8

Fixing solution formulation Ammonium thiosulfate 170 g Sodium sulfite (anhydrous) 15 g Boric acid 7 g Glacial acetic acid 15 ml Potassium alum 20 g Ethylenediaminetetraacetic acid 0.1 g Tartaric acid 3.5 g Add water and 1 liter

The developed and other processed films were measured for optical density with a Fuji automatic densitometer.
The reciprocal of the amount of light required to give an optical density of 2
The relative values are shown assuming that the sensitivity of 01 is 100. Table 6 shows the results.

[0242]

[Table 6]

As is clear from Table 6, the emulsion of the present invention in which the compound represented by the general formula (I) and the compound represented by the general formula (II) were used in combination was used alone or as a compound of the formula (I). (2) high sensitivity and low fog (low residual color) as compared with the emulsion spectrally sensitized with the compound (1) alone. The tendency is remarkable in tabular grains rather than octahedral grains and selenium-sensitized emulsions than sulfur-sensitized emulsions.
In sample 409, extremely high sensitivity and low residual color were realized. As described above, only when the compound of the general formula (I) and the compound of the general formula (II) of the present invention are used at the same time, an emulsion having a specific high sensitivity and low residual color can be obtained. They were found to be more pronounced when combined with grain emulsions and when combined with selenium sensitization.

Example 5 Emulsions 1 to 4 were prepared in the following manner. (1) Preparation of Emulsion 1 An aqueous solution containing gelatin having an average molecular weight of 15,000 (water 12
00ml, gelatin 7.0g, KBr 4.5g)
While keeping the temperature at 30 ° C., a 1.9 M AgNO ₃ aqueous solution and a 1.9 M KBr aqueous solution were added at 25 ml / min for 7 minutes.
The addition was performed by a double jet method for 0 second to obtain nuclei of tabular grains. 400 ml of this emulsion was used as seed crystals, and 650 ml of an inert gelatin aqueous solution (20 g of gelatin, K
(Including 1.2 g of Br) and heated to 75 ° C.
Aged for minutes. Then, an AgNO ₃ aqueous solution (AgNO ₃ 1.
7 g) over 1 minute and 30 seconds, followed by NH 3
₄ 7.0 ml of a NO ₃ (50 wt%) aqueous solution and NH ₃ (25
(wt%) was added and the mixture was aged for an additional 40 minutes. Next, the emulsion was adjusted to pH 7 with HNO ₃ (3N) and KBr
After adding 1.0 g, a 1.9 M AgNO ₃ aqueous solution 36 was added.
6.5 ml of KBr aqueous solution, followed by 1.9 M AgN
53.6 ml of an O ₃ aqueous solution and KBr (KI is 33.3 mol)
An aqueous solution of 1.9 M AgNO ₃ and an aqueous solution of KBr were added while maintaining the pAg at 7.9 to obtain Emulsion 1.

Emulsion 1 obtained was a triple structure grain having a region having the highest silver iodide content in the intermediate shell, an average aspect ratio of 2.8, and a tabular grain having an aspect ratio of 3 or more. The ratio to the total projected area was 26%.
The coefficient of variation of the particle size was 7%, and the average of the particle size was 0.98 μm in sphere equivalent diameter. Emulsion 1 was desalted by a usual flocculation method, and then sensitizing dyes shown in Table 8 were added, and gold, sulfur and selenium sensitization was optimally performed in the presence of the sensitizing dyes.

(2) Preparation of Emulsions 2 and 3 An aqueous solution containing gelatin having an average molecular weight of 15,000 (water 12
00ml, gelatin 7.0g, KBr 4.5g)
While keeping the temperature at 30 ° C., a 1.9 M AgNO ₃ aqueous solution and a 1.9 M KBr aqueous solution were added at 25 ml / min for 7 minutes.
The addition was performed by a double jet method for 0 second to obtain nuclei of tabular grains. 350 ml of this emulsion was used as a seed crystal, and 650 ml of an inert gelatin aqueous solution (20 g of gelatin, K
(Including 1.2 g of Br) and heated to 75 ° C.
Aged for minutes. Then, an AgNO ₃ aqueous solution (AgNO ₃ 1.
7 g) over 1 minute and 30 seconds, followed by NH 3
₄ 6.2 ml of a NO ₃ (50 wt%) aqueous solution and NH ₃ (25
(wt%) was added and the mixture was aged for an additional 40 minutes. This emulsion is designated as A. Emulsion 2 and emulsion 3 were separately formed by performing the subsequent steps in two ways. First, this emulsion A was adjusted to pH 7 with HNO ₃ (3N) and KBr 1.0 g.
Was added, 366.5 m of a 1.9 M AgNO ₃ aqueous solution was added.
1 and a KBr aqueous solution, followed by 53.6 ml of a 1.9 M AgNO ₃ aqueous solution and KBr (containing 33.3 mol% of KI).
Aqueous solution and a 1.9 M AgNO ₃ aqueous solution 160.5
ml and an aqueous KBr solution were added while maintaining the pAg at 8.3 to obtain Emulsion 2. Next, the emulsion A was adjusted to pH 7 with HNO ₃ (3N), and 1.2 g of KBr was added.
366.5 ml of AgNO ₃ aqueous solution and KBr aqueous solution, followed by 53.6 ml of 1.9 MAgNO ₃ aqueous solution and KBr
Aqueous solution (containing 33.3 mol% KI) and
Emulsion 3 was obtained by adding 160.5 ml of a 9M AgNO ₃ aqueous solution and a KBr aqueous solution while maintaining the pAg at 8.8.

Emulsion 2 obtained was a triple structure grain having a region with the highest silver iodide content in the intermediate shell, an average aspect ratio of 6.7, and a tabular grain having an aspect ratio of 6 or more. The ratio of the tabular grains having an aspect ratio of 3 to 100 to the total projected area was 80%, and the ratio to the total projected area was 95%. The coefficient of variation of the particle size is 11
%, And the average particle size is 1.00 μm in sphere equivalent diameter.
Met. Emulsion 3 obtained is a triple structure grain having a region having the highest silver iodide content in the intermediate shell, an average aspect ratio of 8.8, and the total projected area of tabular grains having an aspect ratio of 6 or more. And the proportion of tabular grains having an aspect ratio of 3 or more and 100 or less to the total projected area was 97%. 13% variation coefficient of particle size
The average particle size was 1.13 μm in sphere equivalent diameter.

After Emulsion 2 and Emulsion 3 were desalted by a usual flocculation method, sensitizing dyes shown in Table 8 were added, respectively.
Gold, sulfur and selenium sensitization was performed optimally in that presence.

(3) Preparation of Emulsion 4 A 0.5 M AgNO ₃ solution was added by double jet method to 1.5 liters of a 0.8% low molecular weight (molecular weight 15,000) gelatin solution having 0.05 mol of KBr while stirring. ,
Similarly, 15 ml of a 0.5 M KBr solution is added for 15 seconds. During this time, the gelatin solution was kept at 40 ° C. At this time, the pH of the gelatin solution was 5.0. 7 after addition
The temperature was raised to 5 ° C. After the addition of 220 ml of a 10% trimellitated gelatin (trimellitization rate 95%) solution, the emulsion was ripened for 20 minutes. Then 0.47M Ag
80 ml of the NO ₃ solution was added. After aging for 10 minutes, the KBr solution containing 150 g of AgNO ₃ and 5 mol% of KI for 60 minutes to maintain pBr at 2.55 was accelerated (the flow at the end was the flow at the start). Of 19
X) Controlled double jet method was added while maintaining at 0 mV. After the addition was completed, 30 ml of a 10% KI solution was added. Then, 1N NaOH was added and the pH of the emulsion was adjusted.
Was adjusted to 7.2, and then 327 m of a 0.5 M AgNO ₃ solution
and 16.4 ml of a 10 ^-2 M solution of yellow blood salt were added.
327 ml of a 5M KBr solution was applied at a potential of 0 mV for 20 minutes.
Was added by the control double jet method. (Shell formation) Thereafter, the emulsion was cooled to 35 ° C., washed with water by a usual flocculation method, and 80 g of deionized alkali-treated bone gelatin and 4% of 2% Zn (NO ₃ ) ₂ were added at 40 ° C.
After adding 0 ml and dissolving to adjust the pH to 6.5 and the pAg to 8.6, the mixture was stored in a cool and dark place.

The tabular grains have a projected area equivalent circle diameter (hereinafter referred to as equivalent circle diameter) coefficient of variation of 15%, an equivalent circle diameter of 2.5 μm, and an average thickness of 0.10 μm (aspect ratio). Ratio 25), which was silver iodobromide containing 5.7 mol% of silver iodide. Emulsion 4 was desalted by the usual flocculation method, and the sensitizing dyes shown in Table 8 were added, and gold, sulfur and selenium sensitization was optimally performed in the presence of the sensitizing dyes.

(4) Preparation of Coated Samples Emulsion layers and protective layers as shown in Table 7 were applied to a triacetyl cellulose film support provided with an undercoat layer to prepare samples 501 to 508.

[0252]

[Table 7]

[0253]

Embedded image

Each of these samples was exposed to sensitometry (1/100 second) and subjected to the following color development processing.

Processing method Step Processing time Processing temperature Compensation tank capacity Color development 2 minutes 45 seconds 38 ° C 33 ml 20 liter Bleaching 6 minutes 30 seconds 38 ° C 25 ml 40 liter Rinse 2 minutes 10 seconds 24 ° C 1200 ml 20 liter 4 minutes 20 seconds 38 ° C 25ml 30 liters Washing with water (1) 1 minute 05 seconds 24 ° C 10 liters from (2) to (1) Countercurrent piping system Water washing (2) 1 minute 00 seconds 24 ° C 1200ml 10 liters Constant 1 minute 05 seconds 38 ° C 25 ml 10 liter Drying 4 minutes 20 seconds 55 ° C Replenishment rate per 35 mm width 1 m length Next, the composition of the processing solution is described.

(Color developing solution) Mother liquor (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1.1 1-hydroxyethylidene-1,1-diphosphonic acid 3.0 3.2 Sodium sulfite 4.0 4.4 Potassium carbonate 30.0 37.0 Potassium bromide 1.4 0.7 Iodide Potassium 1.5 mg-hydroxylamine sulfate 2.4 2.8 4- [N-ethyl-N-β-hydroxyethylamino] -2-methylaniline sulfate 4.5 5.5 Add water 1.0 liter 1.0 liter pH 10.05 10.05

(Bleaching solution) Mother liquor (g) Replenisher (g) Ethylenediaminetetraacetic acid sodium ferric trihydrate 100.0 120.0 Ethylenediaminetetraacetic acid disodium salt 10.0 11.0 Ammonium bromide 140.0 160.0 Ammonium nitrate 30.0 35.0 Ammonia water (27%) 6.5 ml 4.0 ml 1.0 liter with water 1.0 liter pH 6.0 5.7

(Fixing solution) Mother solution (g) Replenisher (g) Ethylenediaminetetraacetic acid sodium salt 0.5 0.7 Sodium sulfite 7.0 8.0 Sodium bisulfite 5.0 5.5 Ammonium thiosulfate aqueous solution (70%) 170.0 ml 200.0 ml Add water 1.0 liter 1.0 Liters pH 6.7 6.6

(Stabilizing solution) Mother liquor (g) Replenisher (g) Formalin (37%) 2.0 ml 3.0 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 0.45 Ethylenediaminetetraacetic acid disodium salt 0.05 0.08 1.0 liter with water 1.0 liter pH 5.8-8.0 5.8-8.0

The density of the treated sample was measured with a green filter, and the sensitivity was evaluated. The sensitivity was defined as the reciprocal of the exposure amount giving a density 0.2 higher than the fog density, and the sensitivity of each sample was expressed as a relative value with the value of sample 501 being 100. The emulsion and sensitizing dye used for each sample and the results of the sensitivity of each sample are shown in Table 8 below.

[0261]

[Table 8]

From Table 8, it can be seen that the emulsion of the present invention in which the compound represented by the general formula (I) and the compound represented by the general formula (II) were used in combination only the compound included in the general formula (II) was added. It is apparent that the sensitivity is remarkably improved as compared with the emulsion of the comparative example. Further, the sensitivity becomes higher as the aspect ratio of the emulsion becomes higher. In particular, the sensitivity of the emulsion of the present invention is remarkably improved in tabular grains having an aspect ratio of 8 or more. As described above, only when the compound of the general formula (I) and the compound of the general formula (II) of the present invention are used simultaneously, a silver halide photographic material having high specific sensitivity can be obtained. It has been found that the combination with tabular grains having a high ratio, particularly a combination with tabular grains having an aspect ratio of 8 or more is remarkable.

[0263]

According to the constitution of the present invention, a silver halide photographic emulsion having high dissolution stability over time and a silver halide photographic light-sensitive material having high sensitivity and excellent graininess and having little residual color after processing even in rapid processing. Obtainable.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03C 1/12 G03C 1/12 1/14 1/14 1/16 1/16 1/18 1/18 / / G03C 1/26 1/26

Claims (8)

[Claims] 1. Halogenation of at least one layer on a support
A silver halide photographic light-sensitive material containing a silver photographic emulsion layer
And adding a compound represented by the following general formula (I) to the emulsion layer.
At least one compound represented by the following general formula (II)
Characterized by containing at least one compound
Silver halide photographic material. General formula (I)In the formula (I), Y is an atom group necessary for forming a heterocyclic ring,
Or necessary to form a fused benzene ring with a heterocycle
Group of atoms, fused with another carbocyclic or heterocyclic ring
Or may have a substituent. Z¹And Z^TwoIs
Group of atoms or single bond required to form nitrogen-containing heterocycle
Wherein the nitrogen-containing heterocyclic ring is further
It may be condensed with an elementary ring or may have a substituent. R is
Represents an alkyl group, an aryl group or a heterocyclic group. D is
Represents a group necessary to form a tin dye. L¹And L^Two
Each represents a methine group. p represents 0 or 1. M
Represents a counter ion, and m represents a neutralizing charge in the molecule.
Represents a number of 0 or more required for. General formula (II)In the formula (II), Z³¹And Z³²Forms a nitrogen-containing heterocycle
Represent the group of atoms required for
The aromatic carbocycle may be fused or substituted
However, aromatic or non-aromatic heterocycles may not be fused.
Absent. R³¹And R³²Is an alkyl group, an aryl group or
Represents a heterocyclic group. L³¹, L³², L³³, L ³⁴, L³⁵, L³⁶
And L³⁷Represents a methine group. p³¹And p³²Is 0 or
Represents 1. n^ThreeRepresents 0, 1, 2, 3, or 4. M^Three
Represents a counter ion and m^ThreeNeutralizes the charge in the molecule
Represents a number of 0 or more necessary for 2. In the general formula (I) according to claim 1,
Y forms a pyrrole ring, a furan ring, a thiophene ring, or a pyrrole ring, a furan ring, or a benzene ring condensed with a thiophene ring, which may be condensed with another carbon ring or a heterocyclic ring or may have a substituent. 2. A silver halide photographic light-sensitive material according to claim 1, which represents an atomic group necessary for the formation. 3. The compound represented by the general formula (I) according to claim 1
2. The method according to claim 1, wherein the material is selected from the formula (Ia).
Silver halide photographic material. General formula (Ia)In the formula (Ia), Y¹¹Is pyrrole ring, furan ring, thiophene
Atoms required to form a ring, or indole
Ring, benzofuran ring and benzothiophene ring
Represents a group of atoms necessary for further carbocyclic or heterocyclic rings
And may have a substituent. X¹¹Is an acid
Elementary atom, sulfur atom, selenium atom or NR ¹³Represents R
¹¹, R¹²And R¹³Represents an alkyl group, an aryl group or
Represents a ring group. Z¹¹Is necessary to form a nitrogen-containing heterocycle.
Represents an important group of atoms and is condensed with another carbocyclic or heterocyclic ring.
They may combine or have a substituent. L¹¹, L¹²,
L¹³, L¹⁴And L^FifteenEach represents a methine group. p¹
Represents 0 or 1. n¹Represents 0, 1, 2, 3 or 4
Represent. M¹Represents a counter ion and m¹Neutralizes the charge in the molecule
Represents a number of 0 or more necessary for the 4. The silver halide photographic material according to claim 1, wherein the formula (I) according to claim 1 is selected from the following formula (Ib). General formula (Ib) In the formula (Ib), Y ²¹ represents an atom group necessary for forming a pyrrole ring, a furan ring, and a thiophene ring, and further has a substituent even if fused to another carbon ring or a heterocyclic ring. Is also good. X ²¹ and X ²² represent an oxygen atom, a sulfur atom, a selenium atom or NR ²³ . R ²¹ , R ²² and R ²³ represent an alkyl group, an aryl group or a heterocyclic group. V ^21, V ^22, V
²³ and V ²⁴ represent a hydrogen atom or a substituent, and two adjacent substituents do not combine with each other to form a saturated or unsaturated condensed ring. L ²¹ , L ²² and L ²³ each represent a methine group. n ² represents 0, 1, ² , 3, or 4. M ² represents a counter ion, and m ² represents a number of 0 or more necessary to neutralize the charge in the molecule. 5. The general formula (II) according to claim 1, wherein
2. The method according to claim 1, wherein the compound is selected from the general formula (IIa).
5. The silver halide photographic light-sensitive material according to any one of items 1 to 4. General formula (IIa)In the formula (IIa), X⁴¹And X⁴²Is an oxygen atom, a sulfur atom,
Selenium atom or NR ⁴³Represents V⁴¹, V⁴², V⁴³, V
⁴⁴, V⁴⁵, V⁴⁶, V⁴⁷And V⁴⁸Is a hydrogen atom or substitution
Represents a group in which two adjacent substituents are connected to each other and saturated
Alternatively, an unsaturated condensed ring may be formed. R⁴¹, R⁴²You
And R⁴³Represents an alkyl group, an aryl group or a heterocyclic group.
You. L⁴¹, L⁴²And L⁴³Represents a methine group. n^FourIs
Represents 0, 1, 2, 3, or 4. M^FourIndicates counter ion
Then m^FourIs zero or more necessary to neutralize the charge in the molecule.
Represents the numbers above. 6. The silver halide photograph according to claim 1, wherein the general formula (II) according to claim 1 is selected from the following general formula (III) or (IV). Photosensitive material. General formula (III) In the formula (III), X ⁵¹ and X ⁵² represent an oxygen atom or a sulfur atom. V ⁵¹ , V ⁵² , V ⁵³ , V ⁵⁴ , V ⁵⁵ and V ⁵⁶ represent a hydrogen atom or a substituent, and two adjacent substituents do not combine with each other to form a saturated or unsaturated condensed ring. . R ⁵¹ , R ⁵² and R ⁵³ represent an alkyl group, an aryl group or a heterocyclic group. M ⁵ represents a counter ion and m ⁵
Represents a number of 0 or more necessary for neutralizing the charge in the molecule. General formula (IV) In the formula (IV), X ⁶¹ represents an oxygen atom or a sulfur atom. V
⁶¹ , V ⁶² , V ⁶³ , V ⁶⁴ , V ⁶⁵ and V ⁶⁶ represent a hydrogen atom or a substituent, and two adjacent substituents do not combine with each other to form a saturated or unsaturated condensed ring. R
⁶¹ and R ⁶² represent an alkyl group, an aryl group or a heterocyclic group. M ⁶ represents a counter ion, and m ⁶ represents a number of 0 or more necessary to neutralize the charge in the molecule. 7. The emulsion layer according to claim 1, wherein
7. The silver halide photographic material according to claim 1, wherein 50% or more of the total projected area of the silver halide grains in the emulsion is tabular grains having an aspect ratio of 2 or more. 8. The emulsion layer according to claim 1, wherein
2. The emulsion according to claim 1, wherein the emulsion is selenium-sensitized.
7. The silver halide photographic light-sensitive material according to items 7 to 7.